ES2536738T3 - Cosmetic process using a composition comprising siloxane resins and a powdery coloring matter - Google Patents

Abstract

Cosmetic makeup and/or care procedure for keratinous materials comprising the application on said keratinous materials, mainly on the skin, of a composition comprising, in a physiologically acceptable medium: a) a siloxane resin comprising at least 80% in moles of units: (i) (R'3SiO1/2)a (hereinafter "M" units) and (ii) (SiO4/2)b (hereinafter "Q" units) where - R' independently represents an alkyl group having 1 to 8 carbon atoms, an aryl group, a carbinol group or an amino group, with the proviso that at least 95 mol% of the R' groups are alkyl groups, - a and b have values strictly greater than 0; - and the a/b ratio is between 0.5 and 1.5, b) a propyl silsesquioxane resin comprising at least 80 mol% of (R''SiO3/2) units (hereinafter "T" units ") in which R'' independently represents an alkyl group having 1 to 8 carbon atoms, an aryl group, a carbinol group or an amino group, with the proviso that at least 80 mol% of the R groups '' are propyl groups, the weight ratio between resins a) and b) being between 1/99 and 99/1, in particular between 85/15 and 15/85, resins a) and b) not being linked to one with the other by covalent bonds, and the number of units M of the final mixture being strictly less than the number of units (T+Q), and c) at least one pulverulent coloring matter treated on the surface with a hydrophobic agent chosen from a compound of nature fluorinated, an amino acid, N-acylated amino acids or their salts, and a mixture thereof.

Description

(i)

(R'3SiO1/2)a (de aquí en adelante unidades "M") y

(ii)

(SiO4/2)b (de aquí en adelante unidades "Q")

en las que
 R' representa independientemente un grupo alquilo que tiene de 1 a 8 átomos de carbono, un grupo arilo, un grupo carbinol o un grupo amino,
con la condición de que al menos 95% en moles de los grupos R' son grupos alquilos,
 a y b tienen valores estrictamente superiores a 0;
 y la relación a/b está comprendida entre 0,5 y 1,5,
b) una resina propil silsesquioxano que comprende al menos 80% en moles de unidades (R''SiO3/2) (de aquí en adelante unidades "T") en las que R'' representa independientemente un grupo alquilo que tiene de 1 a 8 átomos de carbono, un grupo arilo, un grupo carbinol o un grupo amino, con la condición de que al menos 80% en moles de los grupos R'' son grupos propilos,
estando comprendida la relación ponderal entre las resinas a) y b) entre 1/99 y 99/1, en particular entre 85/15 y 15/85,
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no estando unidas las resinas a) y b) la una con la otra por enlaces covalentes, y siendo el número de unidades M de la mezcla final estrictamente inferior al número de unidades (T+Q), y c) al menos una materia colorante pulverulenta tratada en superficie por un agente hidrófobo elegido entre un
compuesto de naturaleza fluorada, un aminoácido, aminoácidos N-acilados o sus sales y una de sus mezclas. La presente invención tiene igualmente por objeto un procedimiento cosmético de maquillaje y/o de cuidado de
materias queratínicas que comprende la aplicación sobre dichas materias queratínicas, de una composición que comprende, en un medio fisiológicamente aceptable: a) una resina de siloxano que comprende al menos 80% en moles de unidades:

(i)

(R'3SiO1/2)a (de aquí en adelante unidades "M") y

(ii)

(SiO4/2)b (de aquí en adelante unidades "Q") en las que  R' representa independientemente un grupo alquilo que tiene de 1 a 8 átomos de carbono, un grupo arilo, un

grupo carbinol o un grupo amino, con la condición de que al menos 95% en moles de los grupos R' son grupos alquilos,  a y b tienen valores estrictamente superiores a 0;  y la relación a/b está comprendida entre 0,5 y 1,5, b) una resina propil silsesquioxano filmógena que comprende al menos 80% en moles de unidades (R''SiO3/2) (de
aquí en adelante unidades "T") en las que R'' representa independientemente un grupo alquilo que tiene de 1 a 8 átomos de carbono, un grupo arilo, un grupo carbinol o un grupo amino, con la condición de que al menos 40% en moles de los grupos R'' son grupos propilos,
estando comprendida la relación ponderal entre las resinas a) y b) entre 1/99 y 99/1, en particular entre 85/15 y 15/85, no estando unidas las resinas a) y b) la una con la otra por enlaces covalentes, y siendo el número de unidades M de la mezcla final estrictamente inferior al número de unidades (T+Q),
y c) al menos una materia colorante pulverulenta tratada en superficie por un agente hidrófobo elegido entre un compuesto de naturaleza fluorada, un aminoácido, aminoácidos N-acilados o sus sales y una de sus mezclas.
El procedimiento según la invención permite obtener de manera ventajosa depósitos que tienen una buena
persistencia del color a lo largo de todo el día, y/o una buena homogeneidad del maquillaje. La composición según la invención puede presentarse en diversas formas, principalmente en forma de polvos (libres o compactos), de dispersión anhidra, emulsión agua/aceite o agua/cera, aceite/agua, múltiples o cera/agua, o también en forma de gel.
La composición según la invención está destinada en particular al maquillaje y/o al cuidado de la piel, de los labios, de las uñas, en particular de la piel.
RESINAS DE SILOXANO
La resina de siloxano a), denominada "resina MQ" en lo que sigue, comprende preferentemente grupos silanoles (-SiOH) residuales. En este caso, preferentemente la cantidad de grupos -OH está comprendida entre 2 y 10% en peso de la resina MQ, preferentemente entre 2 y 5% en peso de la resina MQ. Preferentemente, los grupos R' de la resina MQ son grupos Metilo.
La resina b), denominada de aquí en adelante "resina T propilo" comprende preferentemente grupos residuales silanoles (-SiOH) y/o grupos alcoxi. En este caso, preferentemente la cantidad de grupos -OH está comprendida entre 2 y 10% en peso de la resina T propilo, y/o la cantidad de grupos alcoxi es inferior o igual a 20% en peso de la resina T propilo. Preferentemente, la cantidad de grupos -OH está comprendida entre 6 y 8% en peso de la resina T propilo, y/o la cantidad de grupos alcoxi es inferior o igual a 10% en peso de la resina T propilo.
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La resina T propilo según la invención es tal que al menos 40% en moles de los grupos R'' son grupos propilos, preferentemente al menos 50% en moles, y más preferentemente al menos 90% en moles.
Por enlace covalente, se entiende cualquier enlace químico entre al menos 2 átomos (carbono, silicio, oxígeno, etc..) en el que cada uno de los átomos unidos ponen en común un electrón de una de sus capas externas con el fin de formar un doblete de electrones que une los dos átomos.
La resina MQ según la invención comprende al menos 80% en moles de unidades:

(i)

(R'3SiO1/2)a (de aquí en adelante unidades "M") y

(ii)

(SiO4/2)b (de aquí en adelante unidades "Q") en las que  R' representa independientemente un grupo alquilo que tiene de 1 a 8 átomos de carbono, un grupo arilo, un

grupo carbinol o un grupo amino, con la condición de que al menos 95% en moles de los grupos R' son grupos alquilos,  a y b tienen valores estrictamente superiores a 0;  y la relación a/b está comprendida entre 0,5 y 1,5. El radical R' de la resina MQ representa independientemente un grupo alquilo que tiene de 1 a 8 átomos de carbono,
un grupo arilo, un grupo carbinol o un grupo amino.
Los grupos alquilo pueden elegirse principalmente entre los grupos metilo, etilo, propilo, butilo, pentilo, hexilo y octilo. Preferentemente, el grupo alquilo es un grupo metilo o propilo. Los grupos arilo pueden elegirse entre los grupos fenilo, naftilo, bencilo, tolilo, xililo, xenilo, metilfenilo, 2-feniletilo, 2
fenil-2-metiletilo, clorofenilo, bromofenilo y fluorofenilo, siendo el grupo arilo preferentemente un grupo fenilo. En la presente invención, por "grupo carbinol", se entiende cualquier grupo que contiene al menos un radical hidroxilo unido a un carbono (COH). Los grupos carbinol pueden contener así más de un radical COH, tal como por ejemplo imagen1
Si el grupo carbinol está exento de grupos arilo, contiene al menos 3 átomos de carbono. Si el grupo carbinol comprende al menos un grupo arilo, contiene al menos 6 átomos de carbono.
Como ejemplos de grupo carbinol exento de grupos arilo que contienen al menos 3 átomos de carbono, se pueden citar los grupos de fórmula R1OH en la que R1 representa un radical hidrocarbonado bivalente que contiene al menos 3 átomos de carbono o un radical hidrocarbonoxi bivalente que contiene al menos 3 átomos de carbono. Como ejemplos de grupo R1, se pueden citar los radicales alquileno tales como -(CH2)x-, estando comprendido el valor de x entre 3 y 10, -CH2CH(CH3)-, -CH2CH(CH3)CH2-, -CH2CH2CH(CH2CH3)CH2CH2CH2-y -OCH(CH3)(CH2)x-estando comprendido el valor de x entre 1 y 10.
Como ejemplos de grupo carbinol que contiene grupos arilo que presentan al menos 6 átomos de carbono, se pueden citar los grupos de fórmula R2OH en la que R2 representa un radical arileno tal como -(CH2)xC6H4-, teniendo x un valor comprendido entre 0 y 10, -CH2CH(CH3)(CH2)xC6H4-, teniendo x un valor comprendido entre 0 y 10, -(CH2)xC6H4(CH2)x-, teniendo x un valor comprendido entre 1 y 10. Los grupos carbinol que contienen grupos arilo contienen generalmente de 6 a 14 átomos.
Por grupo amino según la invención, se entiende principalmente grupos de fórmula -R3NH2 o -R3NHR4NH2, representando R3 un radical hidrocarbonado bivalente que tiene al menos 2 átomos de carbono y representando R4 un radical hidrocarbonado bivalente que tiene al menos 2 átomos de carbono. El grupo R3 representa generalmente un radical alquileno que tiene de 2 a 20 átomos de carbono. Como ejemplos de grupo R3, se pueden citar los grupos etileno, propileno, -CH2CHCH3-, butileno, -CH2CH(CH3)CH2-, pentametileno, hexametileno, 3-etil-hexametileno, octametileno y decametileno.
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El grupo R4 representa generalmente un radical alquileno que tiene de 2 a 20 átomos de carbono. Como ejemplos de grupo R4, se pueden citar los grupos etileno, propileno, -CH2CHCH3-, butileno, -CH2CH(CH3)CH2-, pentametileno, hexametileno, 3-etil-hexametileno, octametileno y decametileno.
Los grupos amino son generalmente -CH2CH2CH2NH2 y -CH2(CH3)CHCH2(H)NCH3, -CH2CH2NHCH2CH2NH2, -CH2CH2NH2, -CH2CH2NHCH3, -CH2CH2CH2CH2NH2, -(CH2CH2NH)3H y -CH2CH2NHCH2CH2NHC4H9.
Las resinas MQ que convienen para una utilización como componente a), así como sus procedimientos de fabricación, son conocidos en el estado de la técnica. La patente US 2 814 601, que pertenece a Currie et al., fechada el 26 de noviembre 1957 describe un procedimiento de fabricación de resinas MQ por transformación de un silicato hidrosoluble en un monómero de ácido silícico o un oligómero de ácido silícico utilizando un ácido. Una vez se ha realizado la polimerización adecuada, los extremos trimetilclorosilano se introducen para obtener la resina MQ. Otro procedimiento de preparación de resinas MQ se describe en la patente US 2 857 356 que pertenece a Goodwin, fechada el 21 de octubre 1958. Goodwin describe un procedimiento de fabricación de una resina MQ por cohidrólisis de una mezcla de un silicato de alquilo y de un organopolisiloxano trialquilsilano hidrolizable con agua.
Las resinas MQ que convienen como componente a) en la presente invención pueden contener unidades D y T, con la condición de que al menos 80% en moles, incluso 90% en moles de unidades de siloxano totales sean unidades M y Q. Las resinas MQ pueden contener igualmente grupos hidroxi residuales como la mencionada aquí anteriormente. Las resinas MQ pueden contener igualmente extremos suplementarios, haciéndose para esto reaccionar grupos hidroxi residuales con grupos M apropiados.
La resina T propilo b) según la invención comprende al menos 80% en moles de unidades (R''SiO3/2) en las que R'' representa independientemente un grupo alquilo que tiene de 1 a 8 átomos de carbono, un grupo arilo, un grupo carbinol o un grupo amino, con la condición de que al menos 40% en moles de los grupos R'' son grupos propilos.
Preferentemente, la resina T propilo según la invención es tal que al menos 50% en moles de los grupos R'' son grupos propilos, preferentemente al menos 90% en moles.
Preferentemente, la resina T propilo b) es filmógena. Por "resina filmógena", se entiende una resina apta para formar ella sola o en presencia de un agente auxiliar de filmificación, una película macroscópicamente continua y adherente sobre las materias queratínicas, y preferentemente una película cohesiva, y mejor aún una película cuya cohesión y propiedades mecánicas son tales que dicha película puede ser aislada y manipulada aisladamente, por ejemplo cuando dicha película se realiza por acoplamiento sobre una superficie antiadherente como una superficie teflonada
o siliconada.
La definición del radical R'' es la misma que la del radical R'. Las definiciones mencionadas anteriormente aplicables a R' son por lo tanto aplicables a R''.
La resina T propilo b) según la invención es una resina de silsesquioxano. Las resinas de silsesquioxano son muy conocidas en el estado de la técnica y se obtienen generalmente por hidrólisis de un organosilano que contiene tres grupos hidrolizables, tales como grupos halógeno o alcoxi, presentes en la molécula. La resina T propilo b) puede obtenerse así por hidrólisis de propiltrimetoxisilano, propiltrietoxisilano, propiltripropoxisilano, o por cohidrólisis de los propilalcoxisilanos mencionados anteriormente con diversos alcoxisilanos. Como ejemplos de estos alcoxisilanos, se pueden citar metiltrimetoxisilano, metiltrietoxisilano, metiltriisopropoxisilano, dimetildimetoxisilano y feniltrimetoxisilano. El propiltriclorosilano puede hidrolizarse igualmente solo, o en presencia de alcohol. En este caso, la cohidrólisis puede realizarse añadiendo metiltriclorosilano, dimetildiclorosilano, feniltriclorosilano o clorosilanos similares y metiltrimetoxisilano, metiltrietoxisilano, metiltriisopropoxisilano o metilalcoxisilanos similares. Como alcoholes que convienen en este objetivo, se pueden citar metanol, etanol, alcohol n-propílico, alcohol isopropílico, butanol, metoxi etanol, etoxi etanol o alcoholes similares. .Como ejemplos de disolventes de tipo hidrocarburo que pueden utilizarse simultáneamente, se pueden citar tolueno, xileno o hidrocarburos aromáticos similares; hexano, heptano, isooctano o hidrocarburos saturados lineales o en parte ramificados similares; así como ciclohexano o hidrocarburos alifáticos similares.
Las resinas de T propilo b) según la invención pueden contener unidades M, D y Q, con la condición de que al menos 80% en moles, incluso 90% en moles de las unidades de siloxano totales sean unidades T. Las resinas de propilo T pueden contener igualmente grupos hidroxi y/o alcoxi residuales, como la mencionada anteriormente.
La composición según la invención comprende igualmente un medio fisiológicamente aceptable. Por medio fisiológicamente aceptable, se entiende un medio compatible con la piel, las mucosas y los apéndices de la piel.
Este medio puede comprender al menos un disolvente volátil siliconado u orgánico, siendo este disolvente preferentemente compatible con las resinas a/ y b/ y compatible con una utilización cosmética. Como disolvente volátil siliconado, se pueden citar los polisiloxanos cíclicos, polisiloxanos lineales y sus mezclas.
Como polisiloxanos volátiles lineales, se pueden citar hexametildisiloxano, octametiltrisiloxano, decametiltetrasiloxano, tetradecametilhexasiloxano y hexadecametilheptasiloxano. Como polisiloxanos volátiles cíclicos, se pueden citar hexametilciclotrisiloxano, octametilciclotetrasiloxano, decametilciclopentasiloxano y
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dodecametilciclohexasiloxano. El disolvente orgánico puede ser igualmente un alcohol como, etanol, isopropanol, butanol, n-propanol; una cetona como acetona, metiletilcetona, o metil isobutil cetona; un hidrocarburo alifático como heptano, hexano, octano o isododecano; un éter de glicol como éter metílico de propilen glicol, éter metílico de dipropilen glicol, éter n-butílico de propilen glicol, éter n-propílico de propilen glicol, éter n-butílico de etilen glicol.
La mezcla de resinas a/ y b/ puede obtenerse a partir de cada una de las resinas en disolución en un disolvente.
En general, al final de la síntesis de la resina MQ según la invención, se obtiene directamente esta resina en disolución en xileno.
Asimismo, al final de la síntesis de la resina T propilo b) según la invención, se obtiene esta resina en disolución en tolueno.
Cada una de estas resinas en disolución se mezcla con la otra según el protocolo siguiente:
1) Mezclar con agitación las dos disoluciones de resinas, calentar, principalmente en un reactor o en un autoclave (para poder operar eventualmente bajo presión o, al contrario, estableciendo un vacío parcial), incluso en un extrusor equipado o no con un sistema de "desvolatilización" de los disolventes, en las condiciones específicas siguientes:
-se calienta de forma homogénea: la temperatura de calentamiento debe ser superior a 900C, e inferior o igual a 2500C, y preferentemente comprendida entre 900C y 1900C.
Bien se puede calentar a una sola temperatura, comprendida entre 900C y 2500C,
Bien se puede calentar haciendo escalas de temperaturas sucesivas:
en primer lugar entre 900C y T10C,
siendo T10C una temperatura de valor intermedio entre 900C y T20C que es la temperatura final,
durante una duración comprendida entre 10 minutos a 2 horas, y
entre T10C y T20C, durante una duración comprendida entre 10 minutos a 4 horas,
correspondiendo la temperatura T20C a la temperatura máxima elegida para la reacción.
Este valor de T20C es variable según el modo de operación elegido y el tipo de reactor elegido: reactor clásico o autoclave o extrusor, pero T20C permanece inferior o igual a 2500C. Se pueden hacer igualmente escalas de temperaturas intermedias entre T10C y T20C;
-la duración del calentamiento es de al menos una hora en reactor o en autoclave y al menos 10 minutos en extrusor, preferentemente entre 1h y 5h en reactor o en autoclave, y preferentemente entre 10 minutos y 2 horas en extrusor;
-con la condición de que estos tratamientos térmicos se hacen sin presencia de un catalizador de condensación química entre las 2 resinas MQ y T propilo. Un catalizador como éste es principalmente una base mineral, en particular NaOH, KOH o amoniaco.
2) De manera opcional, después, o incluso durante, la etapa 1) de tratamiento térmico de las 2 resinas en el rango de temperatura indicado, se efectúa una destilación parcial o total de los disolventes aromáticos, reemplazándolos por un disolvente volátil cosméticamente aceptable. Un disolvente volátil como éste puede ser principalmente una silicona volátil o no, preferentemente decametilciclopentasiloxano, o un disolvente orgánico volátil o no, preferentemente isododecano.
3) De manera opcional también, después de mezclar las 2 disoluciones iniciales de cada resina en un disolvente volátil, se trata la mezcla de las disoluciones en un mezclador de un tornillo o doble tornillo de tipo extrusor con "desvolatilización" en un rango de temperaturas entre 900C y 2500C, lo que permite volatilizar los disolventes volátiles estableciendo un vacío parcial, trabajando en continuo, y pasar en una terraja la mezcla fundida y sin disolvente. La mezcla fundida se enfría a la salida de la terraja y se recorta en gránulos sólidos o en forma de polvo. En este caso, la mezcla está directamente en forma sólida y se volverá a poner en disolución en los disolventes elegidos en el momento de la formulación.
También la presente invención tiene igualmente por objeto un procedimiento que utiliza una composición tal como la descrita aquí anteriormente que comprende, en un medio fisiológicamente aceptable:
1) la mezcla entre una resina de siloxano a) y una resina de propil silsesquioxano b), siendo la mezcla tal como se describe aquí anteriormente, y
2) al menos una materia colorante pulverulenta tratada en superficie por un agente hidrófobo elegido entre un compuesto de naturaleza fluorada, un ácido graso, un aminoácido y una de sus mezclas,
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formulándose las resinas de siloxano a) y propil silesquioxano b) en la composición mediante una mezcla susceptible de obtenerse según el procedimiento siguiente:
 Mezcla, preferentemente con agitación, de una disolución de resina de siloxano con una disolución de resina propil silsesquioxano, siendo preferentemente el disolvente presente en cada una de las disoluciones volátil, y
 Calentamiento, principalmente en un reactor o en un autoclave o en un extrusor, en las condiciones específicas siguientes:
 se calienta de forma homógenea a una temperatura superior a 900C, e inferior o igual a 2500C, preferentemente
comprendida entre 900C y 1900C; el calentamiento puede hacerse a una sola temperatura, o a escalas de
temperatura, como se indica aquí anteriormente;
 la duración del calentamiento es de al menos 1 hora en reactor o en autoclave y al menos 10 minutos en
extrusor, preferentemente entre 1h y 5h en reactor o en autoclave y preferentemente entre 10 minutos y 2 horas
en extrusor;
 con la condición de que estos tratamientos térmicos se hagan sin presencia de un catalizador de condensación
química entre las 2 resinas MQ y T propilo. Un catalizador como éste es principalmente una base mineral, en
particular NaOH, KOH o amoniaco.
Este procedimiento puede comprender, después o incluso durante la etapa de mezcla, una etapa suplementaria de destilación parcial o total de los disolventes aromáticos, reemplazándolos por un disolvente volátil cosméticamente aceptable.
En el caso en el que se utilice un extrusor, este procedimiento puede comprender, después o incluso durante la etapa de mezcla, una etapa suplementaria de destilación parcial o total de los disolventes aromáticos, saliendo directamente la mezcla en estado sólido.
La etapa final del tratamiento térmico, o incluso el tratamiento térmico él mismo, puede realizarse en un mezclador previsto para la agitación de medios muy viscosos tales como:
 un mezclador de tipo "brazo en Z" ("Zigma blender "), en particular un mezclador Brabender,
 un mezclador con tornillo tipo extrusor, en particular un extrusor mono-tornillo o un extrusor doble tornillo (con o no etapa de "desvolatilización" de los disolventes de partida) o en un mezclador interno que permite desvolatilizar estableciendo una película delgada sobre las paredes.
Las mezclas de resinas 1) utilizables según la invención son principalmente las descritas en la solicitud WO 2005/075567, en particular las descritas en las tablas 1 y 3 de dicha solicitud. Se pueden utilizar igualmente las mezclas de resinas 1) descritas en la solicitud WO2007/145765, en particular las descritas en los ejemplos 12 a 14 de esta solicitud, en las que la relación ponderal entre las resinas a) y b) son respectivamente de 50/50, 60/40 y 71/29 (70/30).
Según un modo particular, se utiliza la mezcla de resinas 1) descrita en el ejemplo 1-f en la tabla 1 de los ejemplos, en la que la relación ponderal entre las resinas a) y b) es de 50/50.
Según un modo particular, se utiliza la mezcla de resinas 1) descrita en el ejemplo 22 de dicha solicitud WO2005/075567, en la que la relación ponderal entre las resinas a) y b) es de 85/15.
Según un modo particular, se utiliza la mezcla de resinas 1) descrita en el ejemplo 13 de dicha solicitud WO2007/145765, en la que la relación ponderal entre las resinas a) y b) es de 60/40.
La relación ponderal entre las resinas a) y b) (es decir, a/b) está comprendida entre 1/99 y 99/1, alternativamente entre 85/15 y 15/85.
La composición según la invención comprende una cantidad de resinas a) y b) de siloxano, en peso de materia activa (materia seca), que va de 0,5 a 60% en peso, respecto al peso total de la composición, preferentemente de 3 a 60% en peso, y mejor de 4 a 60% en peso respecto al peso total de dicha composición.
Según un modo particular, la cantidad de resinas a) y b) de siloxano, en peso de materia activa (materia seca) varía ventajosamente de 3 a 60% en peso, y mejor de 6 a 60% en peso respecto al peso total de dicha composición. Estos contenidos se adaptan principalmente a las composiciones en forma anhidra y en particular a las composiciones en forma de barra, tales como las barras de labios.
Según otro modo particular, la cantidad de resinas a) y b) de siloxano, en peso de materia activa (materia seca) varía ventajosamente de 3 a 30% en peso, y mejor de 4 a 20% en peso respecto al peso total de dicha composición. Estos contenidos se adaptan principalmente a las composiciones en forma de emulsiones, y en particular a las composiciones en forma de emulsiones E/H, tales como las bases de maquillaje líquidas.
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MATERIAS COLORANTES PULVERULENTAS TRATADAS EN SUPERFICIE POR UN AGENTE HIDRÓFOBO
La materia colorante pulverulenta tratada en superficie por un agente hidrófobo puede elegirse entre los pigmentos y/o los nácares.
Por pigmentos, hay que comprender las partículas de cualquier forma, blancas o coloreadas, minerales u orgánicas, insolubles en el medio fisiológico, destinadas a colorear la composición.
Por nácares, hay que comprender las partículas de cualquier forma, irisadas, producidas principalmente por determinados moluscos en su concha o bien sintetizadas.
Los pigmentos pueden ser blancos o coloreados, minerales y/o orgánicos. Se pueden citar, entre los pigmentos minerales, el dióxido de titanio, eventualmente tratado en superficie, los óxidos de circonio o de cerio, así como los óxidos de cinc, de hierro (negro, amarillo o rojo) o de cromo, el violeta de manganeso, el azul ultramar, el hidrato de cromo y el azul férrico, los polvos metálicos como el polvo de aluminio, el polvo de cobre.
Entre los pigmentos orgánicos, se pueden citar el negro de carbón, los pigmentos de tipo D y C, y las lacas a base de carmín de cochinilla, de bario, estroncio, calcio, aluminio.
Se pueden citar igualmente los pigmentos con efecto, tales como las partículas que contienen un sustrato orgánico o mineral, natural o sintético, por ejemplo el vidrio, las resinas acrílicas, el poliéster, el poliuretano, el tereftalato de polietileno, las cerámicas o las alúminas, estando recubierto dicho sustrato o no de sustancias metálicas como el aluminio, el oro, la plata, el platino, el cobre, el bronce, o de óxidos metálicos como el dióxido de titanio, el óxido de hierro, el óxido de cromo y sus mezclas.
Los pigmentos nacarados pueden elegirse entre los pigmentos nacarados blancos tales como la mica recubierta de titanio, o de oxicloruro de bismuto, los pigmentos nacarados coloreados tales como la mica de titanio recubierta con óxidos de hierro, la mica de titanio recubierta principalmente con azul férrico o de óxido de cromo, la mica de titanio recubierta con un pigmento orgánico del tipo precitado así como los pigmentos nacarados a base de oxicloruro de bismuto. Se pueden utilizar igualmente los pigmentos interferenciales, principalmente con cristales líquidos o multicapas.
Las materias colorantes, en particular los pigmentos tratados con un agente hidrófobo, pueden estar presentes en la composición en un contenido que va de 0,1% a 50% en peso, respecto al peso total de la composición, preferentemente que va de 0,5% a 30% en peso, y preferentemente que va de 1% a 20% en peso. Las materias colorantes pulverulentas tratadas en superficie con un agente hidrófobo pueden constituir de 10 a 100% en peso del conjunto de las materias colorantes.
A título ilustrativo de nácares que pueden aplicarse en el marco de la presente invención, se pueden citar principalmente los nácares de color o, principalmente comercializados por la empresa ENGELHARD con el nombre Brillant gold 212G (Timica), GoId 222C (Cloisonne), Sparkle gold (Timica), Gold 4504 (Chromalite) y Monarch gold 233X (Cloisonne); los nácares bronce principalmente comercializados por la empresa MERCK con la denominación Bronze fine (17384) (Colorona) y Bronze (17353) (Colorona) y por la empresa ENGELHARD con la denominación Super bronze (Cloisonne); los nácares naranjas principalmente comercializados por la empresa ENGELHARD con la denominación Orange 363 C (Cloisonne) y Orange MCR 101 (Cosmica) y por la empresa MERCK con la denominación Passion orange (Colorona) y Matte orange (17449) (Microna); los nácares de color marrón principalmente comercializados por la empresa ENGELHARD con la denominación Nu-antique copper 340XB (Cloisonne) y Brown CL4509 (Chromalite); los nácares con reflejo de cobre principalmente comercializados por la empresa ENGELHARD con la denominación Copper 340A (Timica); los nácares con reflejo rojo principalmente comercializados por la empresa MERCK con la denominación Sienna fine (17386) (Colorona); los nácares con reflejo amarillo principalmente comercializados por la empresa ENGELHARD con la denominación Yellow (4502) (Chromalite); los nácares de color rojo con efecto oro principalmente comercializados por la empresa ENGELHARD con la denominación Sunstone G012 (Gemtone); los nácares rosas principalmente comercializados por la empresa ENGELHARD con la denominación Tan opale G005 (Gemtone); los nácares negros con reflejo oro principalmente comercializados por la empresa ENGELHARD con la denominación Nu antique bronze 240 AB (Timica), los nácares azules principalmente comercializados por la empresa MERCK con la denominación Matte blue (17433) (Microna), los nácares blancos con reflejo plateado principalmente comercializados por la empresa MERCK con la denominación Xirona Silver y los nácares anaranjados rosados verde dorado principalmente comercializados por la empresa MERCK con la denominación Indian summer (Xirona) y sus mezclas.
Los nácares tratados en superficie por al menos un agente hidrófobo pueden estar presentes en la composición en un contenido que va de 1 a 50% en peso, respecto al peso total de la composición, mejor de 5 a 30% en peso.
Las materias colorantes pulverulentas tales como las descritas anteriormente se tratan en superficie, totalmente o parcialmente, con un agente hidrófobo: un compuesto de naturaleza fluorada, o aminoácido, o aminoácido N-acilado
o su sal, o una de sus mezclas.
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La presente invención tiene así igualmente por objeto una composición, susceptible de aplicarse en el procedimiento según la invención, que comprende, en un medio fisiológicamente aceptable, las resinas de siloxano a) y b) tales como se han definido aquí anteriormente y al menos una materia colorante pulverulenta tratada en superficie por un agente hidrófobo elegido entre un compuesto de naturaleza fluorada, un aminoácido, o aminoácido N-acilado o su sal, y una de sus mezclas.
Por compuesto de naturaleza fluorada, se entiende un compuesto que comprende al menos un átomo de flúor.
A título de ejemplo, el agente de tratamiento hidrófobo puede elegirse entre los perfluoroalquil fosfatos, los polióxidos de hexafluoropropileno; los perfluoropoliéteres; los aminoácidos; los aminoácidos N-acilados o sus sales y sus mezclas. Preferentemente, el agente de tratamiento hidrófobo puede elegirse entre los perfluoroalquil fosfatos, los polióxidos de hexafluoropropileno; los perfluoropoliéteres; los aminoácidos; los aminoácidos N-acilados o sus sales, y sus mezclas.
Las materias colorantes pulverulentas tratadas en superficie pueden prepararse según técnicas de tratamiento de superficie de naturaleza química, electrónica, mecano-química o mecánica muy conocidas por el experto en la técnica. Se pueden utilizar igualmente productos comerciales.
El agente de superficie puede absorberse o adsorberse sobre las materias colorantes pulverulentas por evaporación del disolvente, reacción química y creación de una unión covalente.
Según una variante, el tratamiento de superficie consiste en un recubrimiento de las materias colorantes pulverulentas.
El recubrimiento puede representar de 1 a 300% en peso del peso de las materias colorantes pulverulentas no tratadas, por ejemplo de 5 a 200%, en particular de 10 a 100% en peso del peso de las materias colorantes pulverulentas no tratadas.
El recubrimiento puede representar de 0,1 a 10% en peso, y en particular de 1 a 5% en peso del peso total de la materia colorante pulverulenta recubierta.
El recubrimiento puede realizarse por ejemplo por adsorción de un agente de superficie líquido en la superficie de las materias colorantes pulverulentas por simple mezcla con agitación de las materias colorantes pulverulentas y de dicho agente de superficie, eventualmente en caliente, previamente a la incorporación de las partículas en los demás ingredientes de la composición de maquillaje o de cuidado.
El recubrimiento puede realizarse por ejemplo por reacción química de un agente de superficie con la superficie de las materias colorantes pulverulentas y creación de una unión covalente entre el agente de superficie y las materias colorantes pulverulentas. Este método se describe principalmente en la patente US 4 578 266.
El tratamiento de superficie químico puede consistir en diluir el agente de superficie en un disolvente volátil, en dispersar las materias colorantes pulverulentas en esta mezcla, y evaporar lentamente el disolvente volátil, de manera que el agente de superficie se deposita en la superficie de las materias colorantes pulverulentas.
Agente de superficie fluorado
Las partículas sólidas pueden tratarse en superficie totalmente o parcialmente con un compuesto de naturaleza fluorada.
Los agentes de superficie fluorados pueden elegirse entre los fosfatos de perfluoroalquilo, los perfluoropoliéteres, los politetrafluoropolietileno (PTFE) y los perfluoroalcanos.
Los perfluoropoliéteres se describen principalmente en la solicitud de patente EP-A-486135, y se venden con las denominaciones comerciales FOMBLIN por la empresa MONTEFLUOS.
Los fosfatos de perfluoroalquilo se describen en particular en la solicitud JP H05-86984. Pueden utilizarse los fosfato-dietanol amina de perfluoroalquilo comercializados por Asahi Glass con la referencia AsahiGuard AG530.
Los perfluoroalcanos pueden ser perfluoroalcanos lineales o cíclicos. Entre los perfluoroalcanos lineales, se puede citar la serie de los alcanos lineales, tales como perfluoroctano, perfluorononano o perfluorodecano. Entre los perfluoroalcanos cíclicos, se pueden citar los perfluorocicloalcanos, perfluoro(alquilcicloalcanos), perfluoropolicicloalcanos, hidrocarburos perfluorados aromáticos (los perfluoroarenos). Entre los perfluoroalcanos, se pueden citar también los compuestos organo perfluorados hidrocarbonados que contienen al menos un heteroátomo.
Entre los perfluorocicloalcanos y los perfluoro(alquilcicloalcanos) se pueden citar la perfluorodecalina vendida con la denominación de "FLUTEC PP5 GMP" por la empresa RHODIA, la perfluoro(metildecalina), los perfluoro(C3-C5 alquil-ciclohexanos) tales como el perfluoro(butilciclohexano).
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Entre los perfluoropolicicloalcanos, se pueden citar los derivados de biciclo [3.3.1] nonano tal como el perfluorotrimetilbiciclo [3.3.1] nonano, los derivados de adamantano, tales como el perfluorodimetiladamantano, y los derivados perfluorados de fenantreno hidrogenado, tales como el tetracosafluoro-tetradecahidrofenantreno.
Entre los perfluoroarenos, se pueden citar los derivados perfluorados de naftaleno, como el perfluoronaftaleno y el perfluorometil-1-naftaleno.
A título de ejemplo de referencias comerciales de pigmentos y de cargas tratadas con un compuesto fluorado, se pueden citar:
-El óxido de hierro amarillo/fosfato de perfluoroalquilo, vendido en particular con la referencia PF 5 Yellow 601 por la empresa Daito Kasei,
-El óxido de hierro rojo/fosfato de perfluoroalquilo, vendido en particular con la referencia PF 5 Red R 516L por la empresa Daito Kasei,
-El óxido de hierro negro/fosfato de perfluoroalquilo, vendido en particular con la referencia PF 5 Black BL 100 por la empresa Daito Kasei,
-El dióxido de titanio/fosfato de perfluoroalquilo, vendido en particular con la referencia PF 5 TiO2 CR 50 por la empresa Daito Kasei,
-El óxido de hierro amarillo/perfluoropolimetilisopropiléter, vendido en particular con la referencia Iran oxyde yellow BF-25-3 por la empresa Toshiki,
-El DC Red 7/perfluoropolimetilisopropiléter, vendido en particular con la referencia D&C Red 7 FHC por la empresa Cardre Inc.,
-El DC Red 6/PTFE, vendido en particular con la referencia T 9506 por la empresa Warner -Jenkinson.
Agente de tratamiento aminoácido
El agente de tratamiento hidrófobo puede elegirse entre los aminoácidos; los aminoácidos N-acilados o sus sales; y sus mezclas.
Los aminoácidos N-acilados pueden comprender un grupo acilo que tiene de 8 a 22 átomos de carbono, como por ejemplo un grupo 2-etil-hexanoílo, caproílo, lauroílo, miristoílo, palmitoílo, estearoílo, cocoílo. Las sales de estos compuestos pueden ser las sales de aluminio, de magnesio, de calcio, de circonio, de cinc, de sodio, de potasio. El aminoácido puede ser por ejemplo la lisina, el ácido glutámico, la alanina.
A título de ejemplo de pigmentos, se pueden citar los vendidos con la referencia comercial NAI -TAO-77891, NAI C33-8073 -10, NAI -C33-8075, NAI -C47-051 -10, NAI -C33-115, NAI -C33-134, NAI -C33-8001-10, NAI -C337001-10, NAI -C33-9001-10 de la empresa MIYOSHI KASEI.
OTROS COMPONENTES
La composición según la invención puede comprender uno o varios componentes adicionales, y en particular componentes elegidos entre los aceites, los tensioactivos no iónicos, los elastómeros siliconados anfífilos, las materias colorantes pulverulentas no tratadas en superficie por un agente hidrófobo, los compuestos pastosos de origen no animal, los agentes reológicos espesantes o gelificantes de fase grasa (en particular con la excepción de los polímeros entrecruzados de dimeticona), las ceras (en particular con la excepción de la cera de candelilla, la ozoquerita y las ceras siliconadas), los agentes gelificantes hidrófilos, las cargas, las materias colorantes pulverulentas no tratadas en superficie por un agente hidrófobo, los polímeros filmógenos, los tensioactivos iónicos (en particular con la excepción de lauril éter sulfato), las fibras, y sus mezclas.
En particular, la composición según la invención puede comprender uno o varios componentes adicionales elegidos entre los aceites, los tensioactivos no iónicos, los elastómeros siliconados anfífilos, las materias colorantes pulverulentas no tratadas en superficie por un agente hidrófobo, los agentes reológicos espesantes o gelificantes de fase grasa (en particular con la excepción de los polímeros entrecruzados de dimeticona), los agentes gelificantes hidrófilos, las cargas, los polímeros filmógenos principalmente lipófilos, y sus mezclas.
Elastómeros de silicona
Las composiciones según la invención pueden comprender además un elastómero de silicona anfífilo, elegido preferentemente entre los elastómeros siliconados polioxialquilenados y poliglicerolados.
Como elastómeros de silicona polioxialquilenados, se pueden citar los descritos en las patentes US5236986, US5412004, US5837793, US5811487.
Como elastómeros de silicona polioxialquilenados, se pueden utilizar:
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-los de nombre INCI PEG-10 Dimethicone/Vinyl dimethicone crosspolymer: como los comercializados con las denominaciones "KSG-21", "KSG-20", por Shin Etsu;
-los de nombre INCI Lauryl PEG-15 Dimethicone/Vinyldimethicone Crosspolymer: como los comercializados con las denominaciones "KSG-30" y "KSG-31", "KSG-32" (en isododecano), "KSG-33" (en trioctanoína), "KSG-210", "KSG310" (en aceite mineral), "KSG-320" (en isododecano), "KSG-330", "KSG-340" por la empresa Shin Etsu.
Como elastómeros de silicona poliglicerolados, se pueden utilizar:
-los de nombre INCI Dimethicone (and) Dimethicone/Polyglycerin-3 crosspolymer: como los comercializados con las denominaciones "KSG-710" por Shin Etsu;
-los de nombre INCI Lauryl Dimethicone/Polyglycerin-3 crosspolymer: como los comercializados con las denominaciones "KSG-840" (en escualeno) por la empresa Shin Etsu.
Estos elastómeros particulares, cuando están en asociación con las resinas según la invención, pueden permitir mejorar las propiedades de no transferencia y de confort (flexibilidad) de las composiciones que los comprenden.
Aceites
La composición según la invención puede comprender además al menos un aceite.
El aceite puede elegirse entre los aceites hidrocarbonados, los aceites siliconados, los aceites fluorados. Estos aceites pueden tener origen animal, vegetal, mineral o sintético.
El aceite puede elegirse entre los aceites volátiles, los aceites no volátiles, y sus mezclas.
Por aceite hidrocarbonado, se entiende un aceite formado esencialmente, incluso constituido, por átomos de carbono y de hidrógeno, y eventualmente átomos de oxígeno, de nitrógeno, y que no contiene átomo de silicio o de flúor; puede contener grupos éster, éter, amina, amida.
Por aceite siliconado, se entiende un aceite que contiene al menos un átomo de silicio, y principalmente que contiene grupos Si-O.
Por aceite fluorado, se entiende un aceite que contiene al menos un átomo de flúor.
La composición según la invención puede comprender al menos un aceite volátil.
Por "aceite volátil", se entiende un aceite (o medio no acuoso) susceptible de evaporarse en contacto con la piel en menos de una hora, a temperatura ambiente y presión atmosférica. El aceite volátil es un aceite cosmético volátil, líquido a temperatura ambiente, que tiene principalmente una presión de vapor no nula, a temperatura ambiente y presión atmosférica, en particular que tiene una presión de vapor que va de 0,13 Pa a 40.000 Pa (10-3 a 300 mm de Hg), y preferentemente que va de 1,3 Pa a 13.000 Pa (0,01 a 100 mm de Hg), y preferentemente que va de 1,3 Pa a
1.300 Pa (0,01 a 10 mm de Hg).
Además, el aceite volátil tiene generalmente un punto de ebullición, medido a presión atmosférica, que va de 1500C a 2600C y preferentemente que va de 1700C a 2500C.
La composición según la invención puede comprender un aceite volátil hidrocarbonado principalmente elegido entre los aceites hidrocarbonados que tienen un punto de inflamabilidad que va de 400C a 1020C, preferentemente que va de 400C a 550C, y preferentemente que va de 400C a 500C.
Como aceite volátil hidrocarbonado, se pueden citar los aceites volátiles hidrocarbonados que tienen de 8 a 16 átomos de carbono y sus mezclas, y principalmente los alcanos ramificados C8-C16 como los iso-alcanos (denominados también isoparafinas) C8-C16, isododecano, isodecano, isohexadecano y por ejemplo los aceites vendidos con los nombres comerciales Isopars o Permetyls, los ésteres ramificados C8-C16 como neopentanoato de iso-hexilo, y sus mezclas. Preferentemente, el aceite volátil hidrocarbonado se elige entre los aceites volátiles hidrocarbonados que tienen de 8 a 16 átomos de carbono y sus mezclas, en particular entre isododecano, isodecano, isohexadecano, y es principalmente isododecano.
Para las buenas propiedades de persistencia del color conservando un depósito mate y confortable para las aplicaciones de color, se preferirán los disolventes volátiles hidrocarbonados de 8 a 16 átomos de carbono, en particular de 9 a 13 átomos de carbono. Como disolvente volátil hidrocarbonado C8 a C16, se pueden citar principalmente los alcanos lineales o ramificados, en particular ramificados, como los iso-alcanos (denominados también isoparafinas) C8-C16, isododecano, isodecano, isohexadecano, y por ejemplo los aceites vendidos con los nombres comerciales Isopars o Permetyls, y sus mezclas. Preferentemente, el disolvente volátil hidrocarbonado que tiene de 8 a 16 átomos de carbono se elige entre isododecano, isodecano, isohexadecano, y su mezcla.
Según un modo de realización particular, el disolvente volátil es isododecano.
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Según otro modo particular de realización, el disolvente volátil hidrocarbonado es un alcano lineal volátil que presenta un punto de inflamabilidad comprendido en el intervalo que varía de 70 a 1200C, y más particularmente de 80 a 1000C, y principalmente es aproximadamente 890C.
Un alcano lineal volátil que conviene a la invención es líquido a temperatura ambiente (aproximadamente 250C). Según un modo de realización, un alcano que conviene a la invención puede ser un alcano lineal volátil que comprende de 8 a 16 átomos de carbono, en particular de 10 a 15 átomos de carbono, y más particularmente de 11 a 13 átomos de carbono.
Un alcano lineal volátil que conviene a la invención puede tener ventajosamente origen vegetal.
Dicho alcano puede obtenerse, directamente o en varias etapas, a partir de una materia prima vegetal como un aceite, una manteca, una cera, etc.
A título de ejemplo de alcano que conviene a la invención, se pueden mencionar los alcanos descritos en la solicitud de patente de la empresa Cognis WO2007/068371.
Estos alcanos se obtienen a partir de alcoholes grasos, ellos mismos obtenidos a partir de aceite de copra o de palma.
A título de ejemplo de alcano lineal que conviene a la invención, se pueden citar n-nonano (C9), n-decano (C10), nundecano (C11), n-dodecano (C12), n-tridecano (C13), n-tetradecano (C14), n-pentadecano (C15), n-hexadecano (C16) y n-heptadecano (C17), y sus mezclas, y en particular la mezcla de n-undecano (C11) y de n-tridecano (C13) comercializado con la referencia CETIOL UT por la empresa Cognis.
Según un modo de realización particular, un alcano lineal volátil que conviene a la invención se puede elegir entre nnonano, n-undecano, n-dodecano, n-tridecano, n-heptadecano, y sus mezclas.
Más particularmente, un alcano lineal volátil que conviene a la invención puede aplicarse en la forma de una mezcla n-undecano/n-tridecano.
Preferentemente, en dicha mezcla, la relación ponderal n-undecano:n-tridecano puede ser 50:50 a 90:10, preferentemente que varía de 60:40 a 80:20, preferentemente que varía de 65:35 a 75:25.
En particular, una composición según la invención puede comprender una mezcla n-undecano:n-tridecano en una relación ponderal de 70:30. Dicha mezcla está comercializada con la denominación CETIOL UT por la empresa COGNIS.
Para los productos de maquillaje de la piel, principalmente las bases de maquillaje y las barras de labios, se utilizarán ventajosamente los aceites volátiles hidrocarbonados lineales que tienen de 8 a 16 átomos de carbono.
Como aceite vegetal siliconado, se pueden citar las siliconas lineales o cíclicas que tienen de 2 a 7 átomos de silicio, conteniendo estas siliconas eventualmente grupos alquilo o alcoxi que tienen de 1 a 10 átomos de carbono. Como aceite de silicona volátil utilizable en la invención, se pueden citar principalmente octametilciclotetrasiloxano, decametilciclopentasiloxano, dodecametilciclohexasiloxano, heptametilhexiltri-siloxano, heptametiloctiltrisiloxano, octametiltrisiloxano, decametiltetrasiloxano y sus mezclas.
El aceite volátil puede estar presente en la composición según la invención en un contenido que va de 0,1% a 90% en peso, respecto al peso total de la composición, preferentemente que va de 1% a 70% en peso, y preferentemente que va de 5% a 50% en peso.
La composición según la invención puede comprender al menos un aceite no volátil.
Por "aceite no volátil", se entiende un aceite que permanece sobre las materias queratínicas a temperatura ambiente y presión atmosférica al menos varias horas y que tiene principalmente una presión de vapor inferior a 10-3 mm de Hg (0,13 Pa). Se puede definir igualmente un aceite no volátil como que tiene una velocidad de evaporación tal que en las condiciones definidas anteriormente, la cantidad evaporada al cabo de 30 minutos es inferior a 0,07 mg/cm2.
Como aceite no volátil hidrocarbonado, se puede utilizar aceite de parafina (o vaselina), escualano, poliisobutileno hidrogenado (aceite de Parleam), perhidroescualeno, aceite de visón, de tortuga, de soja, aceite de almendra dulce, de calophyllum, de palma, de pepitas de uva, de sésamo, de maíz, de arara, de colza, de girasol, de algodón, de albaricoque, de ricino, de aguacate, de jojoba, de oliva o de gérmenes de cereales; ésteres de ácido lanólico, de ácido oleico, de ácido laurico, de ácido esteárico; ésteres grasos, principalmente C12-C36, tales como miristato de isopropilo, palmitato de isopropilo, estearato de butilo, laurato de hexilo, adipato de diisopropilo, isononanoato de isononilo, palmitato de 2-etil-hexilo, laurato de 2-hexil-decilo, palmitato de 2-octil-decilo, miristato o lactato de 2-octildodecilo, succinato de di(2-etil hexilo), malato de diisoestearilo, triisoestearato de glicerina o de diglicerina; ácido behénico, ácido oleico, ácido linoleico, ácido linolénico o ácido isoesteárico; alcoholes grasos superiores, principalmente C16-C22, tales como cetanol, alcohol oleico, alcohol linoleico o linolénico, alcohol isoesteárico u octil dodecanol; y sus mezclas.
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En particular, para obtener un maquillaje que matifica el rostro, conservando un uso confortable, tanto durante la aplicación como después del maquillaje, se utilizarán aceites no volátiles hidrocarbonados C6-C22 que pueden elegirse entre:
-los carbonatos, de fórmula (I) siguiente: R1-O-C(=O)-O-R'1 con R1 y R'1, idénticos o diferentes, que representan una cadena alquilo C4 a C12, y preferentemente C5 a C10, lineal o ramificada, saturada o insaturada (preferentemente saturada), que presenta eventualmente al menos un ciclo, saturado o no, preferentemente saturado;
pudiendo ser estos aceites de fórmula (I) carbonato de dicaprililo, comercializado con la denominación Cetiol CC® por la empresa COGNIS, carbonato de di(etil-2-hexilo), comercializado con la denominación TEGOSOFT DEC® por la empresa Goldschmidt, carbonato de di-isobutirilo; carbonato de di-neopentilo; carbonato de dipentilo; carbonato de di neoheptilo; carbonato de di-heptilo; carbonato de di-isononilo; o carbonato de di-nonilo;
-los monoésteres, de fórmula (II): R2-O-C(=O)-R'2, con R2 y R'2, idénticos o diferentes, que representan una cadena alquilo C4 a C12, y preferentemente C5 a C10, lineal o ramificada, saturada o insaturada (preferentemente saturada), que presenta eventualmente al menos un ciclo, saturado o no, preferentemente saturado;
pudiendo ser estos aceites de fórmula (II) 2-hexil isobutirato de etilo, 2-hexil butirato de etilo, butirato de caprililo, isobutirato de isononilo, 2-hexil hexanoato de etilo, hexanoato de isononilo, hexanoato de neopentilo, heptanoato de caprililo, octanoato de octilo, comercializado con la denominación DRAGOXAT EH® por la empresa SYMRISE, isononanoato de isononilo,
-los di-ésteres de fórmula (III) siguiente: R3-O-C(=O)-R'3-C(=O)-O-R''3, con R3 y R''3, idénticos o diferentes, que representan una cadena alquilo C4 a C12, y preferentemente C5 a C10, lineal o ramificada, saturada o insaturada (preferentemente saturada), que presenta eventualmente al menos un ciclo, saturado o no, preferentemente saturado, y R'3 representa una cadena alquileno, saturada o insaturada, C1 a C4, preferentemente C2 a C4, como por ejemplo una cadena alquileno derivada de succinato (en este caso R'3 es una cadena alquileno C2 saturada), maleato (en este caso R'3 es una cadena alquileno C2 insaturada), glutarato (en este caso R'3 es una cadena alquileno C3 saturada), o adipato (en este caso R'3 es una cadena alquileno C4 saturada); en particular R3 y R''3 se eligen entre isobutilo, pentilo, neopentilo, hexilo, heptilo, neoheptilo, etil 2-hexilo, octilo, nonilo, isononilo; se pueden citar preferentemente maleato de dicaprililo, principalmente comercializado por la empresa ALZO; succinato de di(2etil hexilo);
-los éteres, de fórmula siguiente (IV): R4-O-R4', con R4 y R4', idénticos o diferentes, que representan una cadena alquilo C4 a C12, y preferentemente C5 a C10, lineal o ramificada, saturada o insaturada (preferentemente saturada), que presenta eventualmente al menos un ciclo, saturado o no, preferentemente saturado; en particular R4 y R4' se eligen entre isobutilo, pentilo, neopentilo, hexilo, heptilo, neoheptilo, etil 2-hexilo, octilo, nonilo, isononilo; entre los compuestos e fórmula (IV), se pueden citar preferentemente éter de dicaprililo, comercializado con el nombre de Cetiol OE® por la empresa COGNIS;
-los tri-ésteres de alquilos de fórmula (V): R5-O-C(O)-CH2-CH[-O-C(O)-R'5]-CH2-O-C(O)-R''5, con R5, R'5 y R''5, idénticos o diferentes, que representan una cadena alquilo C4-C10, preferentemente C5-C8, lineal o ramificada, saturada o insaturada (preferentemente saturada), en particular R5, R'5 y R''5 son idénticos; preferentemente R5, R'5 y R''5 (en particular idénticos) son radicales alquilos de ácidos grasos siguientes: ácido caprílico, etil-2-hexílico, neopentanoico, o neoheptanoico; se puede citar preferentemente, como compuesto de fórmula (V), triglicérido caprílico cáprico, comercializado principalmente con el nombre MYRITOL 318® por la empresa COGNIS;
-y sus mezclas.
El aceite no volátil hidrocarbonado C6-C22 utilizado ventajosamente en dichas composiciones de maquillaje y/o de cuidado destinadas a matificar el rostro es carbonato de dicaprililo, principalmente comercializado con el nombre de CETIOL CC por la empresa COGNIS.
Ventajosamente, cuando la composición está destinada al maquillaje y/o al cuidado de los labios y comprende un aceite no volátil, este aceite se elige entre los aceites siliconados fenilados. Dicho aceite se denomina igualmente silicona fenilada.
Se entiende por silicona fenilada, un organopolisiloxano sustituido con al menos un grupo fenilo. La silicona fenilada es preferentemente no volátil. Por "no volátil", se entiende un aceite cuya presión de vapor a temperatura ambiente y presión atmosférica, es no nula e inferior a 0,13 Pa.
Preferentemente, el peso molecular en peso del aceite siliconado fenilado está comprendido entre 500 y 10.000 g/mol.
El aceite siliconado puede elegirse entre las fenil trimeticonas, fenil dimeticonas, fenil trimetilsiloxi difenilsiloxanos, difenil dimeticonas, difenil metildifenil trisiloxanos, 2-feniletil trimetilsiloxisilicatos.
El aceite siliconado puede responder a la fórmula:
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en la que los grupos R representan independientemente los unos de los otros un metilo o un fenilo. Preferentemente en esta fórmula, el aceite siliconado comprende al menos tres grupos fenilo, por ejemplo al menos cuatro, al menos cinco o al menos seis.
Según otro modo de aplicación, el aceite siliconado responde a la fórmula imagen3
en la que los grupos R representan independientemente los unos de los otros un metilo o un fenilo. Preferentemente en esta fórmula, dicho organopolisiloxano comprende al menos tres grupos fenilos, por ejemplo al menos cuatro o al menos cinco.
10 Pueden utilizarse mezclas de los organopolisiloxanos fenilados descritos anteriormente. Se pueden citar por ejemplo mezclas de organopolisiloxano trifenilado, tetra o penta-fenilado. Según otro modo de aplicación, el aceite siliconado responde a la fórmula imagen4
en la que Me representa metilo, Ph representa fenilo. Dicha silicona fenilada la fabrica principalmente Dow Corning 15 con la referencia Dow Corning 555 Cosmetic Fluid (nombre INCI: trimethyl pentaphenyl trisiloxane). También puede utilizarse la referencia Dow Corning 554 Cosmetic Fluid.
Según otro modo de aplicación, el aceite siliconado responde a la fórmula imagen5
en la que Me representa metilo, y está comprendido entre 1 y 1.000, y X representa -CH2-CH(CH3)(Ph). 20 Según otro modo de aplicación, el aceite siliconado responde a la fórmula
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en la que -OR' representa -O-SiMe3, y está comprendido entre 1 y 1.000 y z está comprendido entre 1 y 1.000. El aceite siliconado fenilado puede elegirse entre las siliconas feniladas de fórmula (VI) siguiente: imagen7
5 en la que
-R1 a R10, independientemente los unos de los otros, son radicales hidrocarbonados, saturados o insaturados, lineales, cíclicos o ramificados, C1-C30, -m, n, p y q son, independientemente los unos de los otros, números enteros comprendidos entre 0 y 900, con la
reserva de que la suma "m+n+q" es diferente de 0.
10 Preferentemente, la suma "m+n+q" está comprendida entre 1 y 100. Preferentemente, la suma "m+n+q" está comprendida entre 1 y 900, incluso mejor entre 1 y 800. Preferentemente, q es igual a 0. El aceite siliconado fenilado puede elegirse entre las siliconas feniladas de fórmula (VII) siguiente: imagen8
en la que:
15 -R1 a R6, independientemente los unos de los otros, son radicales hidrocarbonados, saturados o insaturados, lineales, cíclicos o ramificados, C1-C30,
-m, n y p son, independientemente los unos de los otros, números enteros comprendidos entre 0 y 100, con la reserva de que la suma "n+m" está comprendida entre 1 y 100.
Preferentemente, R1 a R6, independientemente los unos de los otros, representan un radical hidrocarbonado 20 saturado, lineal o ramificado, C1-C30, principalmente C1-C12, y en particular un radical metilo, etilo, propilo o butilo.
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Principalmente, R1 a R6 pueden ser idénticos, y además pueden ser un radical metilo.
Preferentemente, se puede tener m= 1 ó 2 ó 3, y/o n= 0 y/o p= 0 ó 1, en la fórmula (VII).
Se puede utilizar un aceite siliconado fenilado de fórmula (VI) que tiene una viscosidad a 250C comprendida entre 5 y 1.500 mm2/s (es decir, 5 a 1.500 cSt), preferentemente que tiene una viscosidad comprendida entre 5 y 1.000 mm2/s (es decir, 5 a 1.000 cSt).
Como aceite siliconado fenilado de fórmula (VII), se pueden utilizar principalmente las feniltrimeticonas tales como la DC556 de Dow Corning (22,5 cSt), el aceite Silbione 70663V30 de Rhône Poulenc (28 cSt), o las difenildimeticonas tales como los aceites Belsil, principalmente Belsil PDM1000 (1.000 cSt), Belsil PDM 200 (200 cSt) y Belsil PDM 20 (20 cSt) de Wacker. Los valores entre paréntesis representan las viscosidades a 250C.
El aceite siliconado no volátil puede elegirse entre las siliconas de fórmula: imagen9
en la que:
R1, R2, R5 y R6 son, conjuntamente o separadamente, un radical alquilo que tiene 1 a 6 átomos de carbono,
R3 y R4 son, conjuntamente o separadamente, un radical alquilo que tiene de 1 a 6 átomos de carbono, o un radical arilo,
X es un radical alquilo que tiene de 1 a 6 átomos de carbono, un radical hidroxilo o un radical vinilo,
eligiéndose n y p de manera que confieran al aceite una masa molecular en peso inferior a 200.000 g/mol, preferentemente inferior a 150.000 g/mol y más preferentemente inferior a 100.000 g/mol.
El aceite no volátil puede estar presente en un contenido que va de 0,1% a 70% en peso, respecto al peso total de la fase grasa líquida no volátil, preferentemente que va de 0,5% a 60% en peso, y preferentemente que va de 1% a 50% en peso.
Para los productos de maquillaje de la piel, principalmente las bases de maquillaje y las barras de labios, se utilizarán ventajosamente los aceites de siliconas lineales volátiles o no volátiles. La asociación de las resinas según la invención y de un aceite siliconado lineal puede permitir principalmente mejorar la no transferencia.
Para los productos de maquillaje de la piel, principalmente las barras de labios, se utilizarán ventajosamente los aceites de siliconas feniladas. La asociación de las resinas según la invención y de un aceite siliconado fenilado puede permitir principalmente mejorar la brillantez, el confort y disminuir la sensación de pegajoso.
Tensioactivos no iónicos
La composición según la invención puede comprender al menos un tensioactivo no iónico.
En particular, se puede utilizar un emulsionante que posea a 250C un equilibrio HLB (equilibrio hidrófilo-lipófilo) según GRIFFIN, específico de la composición que se desea obtener. El valor HLB según GRIFFIN se define en J. Soc. Cosm. Chem. 1954 (volumen 5), páginas 249-256. Se puede hacer referencia al documento "Encyclopedia of Chemical Technology, KIRK-OTHMER", volumen 22, p. 333-432, 3ª edición, 1979. WILEY, para la definición de las propiedades y de las funciones (emulsionante) de los tensioactivos, en particular p. 347-377 de esta referencia, para los tensioactivos no iónicos.
Los tensioactivos no iónicos utilizados preferentemente en la composición según la invención se eligen entre:
a) los tensioactivos no iónicos de HLB superior o igual a 8 a 250C, utilizados solos o mezclados; se pueden citar principalmente:
-los ésteres y éteres de osas tales como la mezcla de cetilestearil glucósido y de alcoholes cetílico y estearílico como Montanov 68 de Seppic;
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-los éteres oxietilenados y/o oxipropilenados (que pueden contener de 1 a 150 grupos oxietilenados y/o oxipropilenados) de glicerol;
-los éteres oxietilenados y/o oxipropilenados (que pueden contener de 1 a 150 grupos oxietilenados y/o oxipropilenados) de alcoholes grasos (principalmente de alcohol C8-C24, y preferentemente C12-C18) tales como éter oxietilenado de alcohol cetearílico con 30 grupos oxietilenados (nombre CTFA "Ceteareth-30"), éter oxietilenado de alcohol estearílico con 20 grupos oxietilenados (nombre CTFA "Steareth-20"), y éter oxietilenado de mezcla de alcoholes grasos C12-C15 que contiene 7 grupos oxietilenados (nombre CTFA "C12-C15 Pareth-7") comercializado con la denominación NEODOL 25-7® por SHELL CHEMICALS,
-los ésteres de ácido graso (principalmente de ácido C8-C24, y preferentemente C16-C22) y de polietilen glicol (que pueden comprender de 1 a 150 restos de etilenglicol) tales como estearato de PEG-50 y monoestearato de PEG-40 comercializado con el nombre MYRJ 52P® por la empresa ICI UNIQUEMA,
-los ésteres de ácido graso (principalmente de ácido C8-C24, y preferentemente C16-C22) y los éteres de glicerol oxietilenados y/o oxipropilenados (que pueden contener de 1 a 150 grupos oxietilenados y/o oxipropilenados), como el monoestearato de PEG200 glicerilo vendido con la denominación Simulsol 220 TM® por la empresa SEPPIC; el estearato de glicerilo polietoxilado con 30 grupos de óxido de etileno como el producto TAGAT S® vendido por la empresa GOLDSCHMIDT, el oleato de glicerilo polietoxilado con 30 grupos de óxido de etileno como el producto TAGAT O® vendido por la empresa GOLDSCHMIDT, el cocoato de glicerilo polietoxilado con 30 grupos de óxido de etileno como el producto VARIONIC LI 13® vendido por la empresa SHEREX, el isoestearato de glicerilo polietoxilado con 30 grupos de óxido de etileno como el producto TAGAT L® vendido por la empresa GOLDSCHMIDT y el laurato de glicerilo polietoxilado con 30 grupos de óxido de etileno como el producto TAGAT I® de la empresa GOLDSCHMIDT.,
-los ésteres de ácido graso (principalmente de ácido C8-C24, y preferentemente C16-C22) y los éteres de sorbitol oxietilenados y/o oxipropilenados (que pueden contener de 1 a 150 grupos oxietilenados y/o oxipropilenados), como el polisorbato 20 vendido con la denominación Tween 20® por la empresa CRODA, el polisorbato 60 vendido con la denominación Tween 60® por la empresa CRODA,
-la dimeticona copoliol, tal como la vendida con la denominación Q2-5220® por la empresa DOW CORNING,
-la dimeticona copoliol benzoato (FINSOLV SLB 101® y 201® de la empresa FINTEX),
-los copolímeros de óxido de propileno y de óxido de etileno, igualmente denominados policondensados OE/OP,
-y sus mezclas.
Los policondensados OE/OP son más particularmente copolímeros que consisten en bloques de polietilen glicol y propilen glicol, como por ejemplo los policondensados tribloque polietilen glicol/polipropilen glicol/polietilen glicol. Estos policondensados tribloque tienen por ejemplo la estructura química siguiente: imagen10
fórmula en la que a va de 2 a 120, y b va de 1 a 100.
El policondensado OE/OP tiene preferentemente un peso molecular medio en peso que va de 1.000 a 15.000, y mejor que va de 2.000 a 13.000. Ventajosamente, dicho policondensado OE/OP tiene una temperatura de turbidez, a 10 g/l en agua destilada, superior o igual a 200C, preferentemente superior o igual a 600C. La temperatura de turbidez se mide según la norma ISO 1065. Como policondensado OE/OP utilizable según la invención, se pueden citar los policondensados tribloque polietilen glicol/polipropilen glicol/polietilen glicol vendidos con las denominaciones SYNPERONIC® como SYNPERONIC PE/L44® y SYNPERONIC PE/F127® por la empresa ICI.
b) los tensioactivos no iónicos de HLB inferior a 8 a 250C, eventualmente asociados a uno o varios agentes tensioactivos no iónicos de HLB superior a 8 a 250C, tales como los citados anteriormente tales como:
-los ésteres y éteres de osas tales como estearato de sacarosa, cocoato de sacarosa, estearato de sorbitán y sus mezclas como Arlatone 2121® comercializado por la empresa ICI;
-los éteres oxietilenados y/o oxipropilenados (que pueden contener de 1 a 150 grupos oxietilenados y/o oxipropilenados) de alcoholes grasos (principalmente de alcohol C8-C24, y preferentemente C12-C18) tales como éter oxietilenado de alcohol estearílico con 2 grupos oxietilenados (nombre CTFA "Steareth-2");
-los ésteres de ácidos grasos (principalmente de ácido C8-C24, y preferentemente C16-C22) y de poliol, principalmente de glicerol o de sorbitol, tales como estearato de glicerilo, estearato de glicerilo de tal como el producto vendido con la denominación TEGIN M® por la empresa GOLDSCHMIDT, laurato de glicerilo tal como el producto vendido con la denominación IMWITOR 312® por la empresa HULS, estearato de poligliceril-2, triestearato de sorbitán, ricinoleato de glicerilo;
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-las lecitinas, tales como las lecitinas de soja (como Emulmetik 100 J de Cargill, o Biophilic H de Lucas Meyer);
-la mezcla de ciclometicona/dimeticona copoliol vendida con la denominación Q2-3225C® por la empresa DOW CORNING. El tensioactivo no iónico también puede elegirse entre un alquil C8-C22 dimeticona copoliol, es decir, un poli metil
alquil(C8-C22) dimetil metil siloxano oxipropilenado y/o oxietilenado. El alquil C8-C22 dimeticona copoliol es ventajosamente un compuesto de fórmula (I) siguiente: imagen11
en la que:
-PE representa (-C2H4O)x-(C3H6O)y-R, eligiéndose R entre un átomo de hidrógeno y un radical alquilo de 1 a 4 átomos de carbono, yendo x de 0 a 100 y yendo y de 0 a 80, no siendo x e y simultáneamente 0 -yendo m de 1 a 40 -yendo n de 10 a 200 -yendo o de 1 a 100 -yendo p de 7 y 21 -yendo q de 0 a 4 y preferentemente R= H, m= 1 a 10; n= 10 a 100; o= 1 a 30; p= 15; y q= 3. Como alquil C8-C22 dimeticona copoliol, se puede citar el cetil dimeticona copoliol como el producto comercializado
con la denominación Abil EM-90 por la empresa Goldschmidt. Según un modo particular destinado a formular emulsiones estables, que presentan una viscosidad baja que permite una aplicación fácil, confiriendo al producto de maquillaje una persistencia en el tiempo de maquillaje una vez
aplicado, se utilizará ventajosamente al menos un tensioactivo no iónico siliconado, eventualmente asociado al menos a un tensioactivo hidrocarbonado y eventualmente además al menos una cera: Como tensioactivo siliconado no iónico, se puede citar por ejemplo: a) las polidialquil siliconas con grupos laterales y/o terminales hidrófilos polioxialquilenados (polioxietilenados (o
POE) y/o polioxipropilenados (o PPO). Además, estos tensioactivos siliconados contienen, preferentemente, grupos laterales alquilos C1 a C20 lineales o ramificados, preferentemente grupos alquilos lineales, tales como laurilo o cetilo. Estos tensioactivos pueden portar también grupos laterales organosiloxanos.
En particular, en esta primera categoría, se pueden citar:
-los polidimetil siloxanos con grupos laterales POE, tales como principalmente KF-6011, KF-6012, KF-6013, KF6015, KF-6016 y KF-6017 de la empresa Shin Etsu.; -los polidimetil siloxanos con grupos laterales POE y con grupos laterales alquilos, tales como principalmente Cetil
PEG-PPG 10/1 dimeticona, comercializado con la denominación ABIL EM90 por la empresa Evonik
GOLDSCHMIDT; -los polidimetilsiloxanos ramificados con grupos laterales POE, tales como principalmente PEG-9 polidimetil siloxietil dimeticona, comercializado con la denominación KF-6028 por la empresa Shin Etsu;
-los polidimetil siloxanos ramificados con grupos laterales alquilos, tales como principalmente lauril PEG-9 polidimetilsiloxietil dimeticona, comercializado con la denominación KF-6038 por la empresa Shin Etsu.
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b) las polidialquil siliconas con grupos laterales poliglicerolados o glicerolados. Estos tensioactivos siliconados contienen además, preferentemente, grupos laterales alquilos C1 a C20 lineales o ramificados, y preferentemente también grupos alquilos lineales tales como laurilo o cetilo. Asimismo, estos tensioactivos siliconados y glicerolados pueden, además, portar grupos laterales organosiloxanos.
En particular en esta categoría, se pueden citar:
-los polidimetil siloxanos con grupos laterales poliglicerolados, tal como poligliceril -3 disiloxano dimeticona, comercializado con la denominación KF-6100 por la empresa Shin Etsu;
-los polidimetil siloxanos ramificados y con grupos laterales poliglicerolados, tal como poligliceril -3 polidimetilsiloxietil dimeticona, comercializado con la denominación KF-6104 por la empresa Shin Etsu;
-los polidimetil siloxanos ramificados, con grupos laterales poliglicerolados y con grupos laterales alquilos, tal como lauril poligliceril -3 polidimetil siloxietil dimeticona, comercializado con la denominación KF-6105 por la empresa Shin Etsu.
Entre los tensioactivos no iónicos siliconados, se prefiere Cetil PEG/PPG -10/1 dimeticona, comercializado con la denominación ABIL EM90 por la empresa EVONIK GOLDSCHMIDT.
El tensioactivo siliconado no iónico está ventajosamente en asociación con al menos un tensioactivo orgánico no iónico.
Como tensioactivo orgánico no iónico, se puede citar los ésteres de ácidos grasos de polioles como los mono, di, tri
o sesqui-oleatos o estearatos de sorbitol o de glicerol, los lauratos de glicerol o de polietilen glicol; los ésteres de ácidos grasos de polietilen glicol (monoestearato o monolaurato de polietilen glicol); los ésteres de ácidos grasos (estearato, oleato) de sorbitol polioxietilenados; los alquil (lauril, cetil, estearil, octil) éteres polioxietilenados.
Entre los tensioactivos orgánicos no iónicos, se prefiere:
-los ésteres de ácidos grasos poliglicerolados que contienen al menos 3 restos glicerol éter, tal como poligliceril 3;
-los ésteres de ácidos grasos polioxialquilenados (polioxietilenados y/o polioxipropilenados), que contienen preferentemente al menos 3 grupos oxietileno;
-los éteres de alcoholes grasos y de poligliceroles con al menos 3 restos éter de glicerilo;
-los éteres de alcoholes grasos y de polioxialquileno (POE y/o POE/PPO) con al menos 3 grupos POE.
Entre los tensioactivos orgánicos no iónicos, se prefiere el poligliceril-4-isoestearato comercializado con la denominación ISOLAN GI34® por la empresa EVONIK GOLDSCHMIDT.
En asociación con el tensioactivo siliconado no iónico y el tensioactivo orgánico no iónico, se podrá utilizar ventajosamente al menos una cera.
Entre las ceras, se prefiere la mezcla de estearato de etilen glicol acetil/tri-estearato de glicerilo, principalmente comercializado con la denominación UNITWIX por la empresa UNITED GARDIAN.
Agente reológico espesante o gelificante de fase grasa
La composición según la invención puede comprender además un agente reológico espesante o gelificante de fase grasa.
Se entiende por "agente reológico espesante o gelificante de fase grasa" un compuesto apto para aumentar la viscosidad de la fase grasa de la composición. El agente reológico espesante o gelificante de fase grasa permite principalmente obtener una composición que puede presentar una textura que va de texturas fluidas a sólidas.
Preferentemente, los agentes reológicos espesantes o gelificantes de fase grasa se eligen entre los polímeros cristalinos, agentes estructurantes lipófilos minerales, poliamidas lipófilas, poliureas y poliuretanos lipófilos, polímeros siliconados que comprenden llegado el caso al menos un resto hidrocarbonado que contiene dos grupos capaces de establecer interacciones de hidrógeno elegidas entre los grupos éster, amida, sulfonamida, carbamato, tiocarbamato, urea, uretano, tiourea, oxamido, guanidino, biguanidino y sus combinaciones, organogelantes, polímeros de bloques, agentes de cristales líquidos colestéricos, copolímeros dimeticona/vinildimeticona, y copolímeros vinildimeticona/alquil dimeticona, tales como copolímeros vinildimeticona/lauril dimeticona.
El agente reológico espesante o gelificante de fase grasa puede elegirse entre:
-los polímeros cristalinos, preferentemente elegidos entre los polímeros semi-cristalinos, ésteres de dextrina y de ácido graso, polisacáridos modificados hidrófobos, copolímeros de olefinas cristalinos y policondensados cristalinos;
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-los agentes estructurantes lipófilos minerales, como las arcillas lipófilas y las sílices hidrófobas, como la sílice pirogenada tratada hidrófoba,
-los polímeros de tipo poliamida lipófilos,
-las poliureas y los poliuretanos lipófilos,
-los polímeros siliconados que comprenden llegado el caso al menos un resto hidrocarbonado que contiene dos grupos capaces de establecer interacciones de hidrógeno elegidas entre los grupos éster, amida, sulfonamida, carbamato, tiocarbamato, urea, uretano, tiourea, oxamido, guanidino, biguanidino y sus combinaciones, preferentemente grupos amidas,
-los organogelantes;
-los polímeros de bloques;
-los agentes de cristales líquidos colestéricos;
-los elastómeros de silicona;
-y sus mezclas.
Preferentemente, el agente reológico de fase grasa se elige entre los polímeros semi-cristalinos, polímeros de bloques, polímeros de tipo poliamida lipófilos, y polímeros siliconados que comprenden al menos un resto hidrocarbonado que contiene dos grupos capaces de establecer interacciones de hidrógeno elegidas entre los grupos amidas, agentes estructurantes lipófilos minerales, en particular arcillas lipófilas y las sílices hidrófobas, y los elastómeros de silicona.
Se precisa que, según la invención, en el caso de las asociaciones de un agente reológico de fase grasa con un aceite, se entiende por "aceite" un cuerpo graso líquido a temperatura ambiente. Los aceites pueden ser los descritos anteriormente.
Agentes estructurantes lipófilos minerales
El agente reológico espesante o gelificante de fase grasa puede ser un agente estructurante lipófilo mineral.
Se pueden citar principalmente las arcillas lipófilas, como las arcillas eventualmente modificadas tales como los hectoritos modificados por un cloruro de amonio de ácido graso C10 a C22, como hectorito modificado por cloruro de di-estearil di-metil amonio.
Las arcillas son silicatos que contienen un catión que puede elegirse entre los cationes de calcio, de magnesio, de aluminio, de sodio, de potasio, de litio, y sus mezclas.
A título de ejemplos de dichos productos, se pueden citar las arcillas de la familia de las esmectitas tales como montmorilonitas, hectoritos, bentonitas, beidelitas, saponitas, así como de la familia de las vermiculitas, estevensita, cloritos. Estas arcillas pueden tener origen natural o sintético.
La arcilla puede elegirse entre montmorilonita, bentonita, hectorito, atapulgita, sepiolita, y sus mezclas. La arcilla es preferentemente una bentonita o un hectorito.
Las arcillas organófilas son arcillas modificadas con un compuesto químico elegido entre las aminas cuaternarias, aminas terciarias, acetatos aminados, imidazolinas, jabones aminados, sulfatos grasos, alquil aril sulfonatos, óxidos aminados, y sus mezclas.
Como arcillas organófilas, se pueden citar las cuaternio-18 bentonitas tales como las vendidas con las denominaciones Bentone 3, Bentone 38, Bentone 38V por la empresa Elementis, Tixogel VP por la empresa United catalyst, Claytone 34, Claytone 40, Claytone XL por la empresa Southern Clay; las estearalconio bentonitas tales como las vendidas con las denominaciones Bentone 27V por la empresa Elementis, Tixogel LG por la empresa United Catalyst, Claytone AF, Claytone APA por la empresa Southern Clay; las cuaternio-18/benzalconio bentonita tales como las vendidas con las denominaciones Claytone HT, Claytone PS por la empresa Southern Clay.
Según un modo de realización preferido, el agente espesante se elige entre las arcillas modificadas organófilas, tales como hectorito modificado por estearato de bencildimetilamonio.
Se pueden citar igualmente las sílices hidrófobas, como la sílice pirogenada eventualmente tratada hidrófoba en superficie cuyo tamaño de partículas es inferior a 1 μm. Es en efecto posible modificar químicamente la superficie de la sílice, por reacción química que genera una disminución del número de grupos silanol presentes en la superficie de la sílice. Se pueden sustituir principalmente grupos silanol por grupos hidrófobos: se obtiene una sílice hidrófoba. Los grupos hidrófobos pueden ser:
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-grupos trimetilsiloxilo, que se obtienen principalmente por tratamiento de sílice pirogenada en presencia de hexametildisilazano. Las sílices así tratadas se denominan "Silica silylate " según CTFA (6ª edición, 1995). Se comercializan, por ejemplo, con las referencias "AEROSIL R812®" por la empresa Degussa, "CAB-O-SIL TS-530®" por la empresa Cabot.
-grupos dimetilsililoxilo o polidimetilsiloxano, que se obtienen principalmente por tratamiento de sílice pirogenada en presencia de polidimetilsiloxano o de dimetildiclorosilano. Las sílices así tratadas se denominan "Silica dimethyl silylate " según CTFA (6ª edición, 1995). Se comercializan, por ejemplo, con las referencias "AEROSIL R972®", "AEROSIL R974®" por la empresa Degussa, "CAB-O-SIL TS-610®", "CAB-O-SIL TS-720®" por la empresa Cabot.
La sílice pirogenada hidrófoba presenta preferentemente un tamaño de partículas que puede ser nanométrico a micrométrico, por ejemplo, que va de aproximadamente 5 a 200 nm.
Polímeros poliamidas lipófilos
Por polímero, se entiende en el sentido de la invención un compuesto que tiene al menos 2 restos de repetición, preferentemente al menos 3 restos de repetición y mejor aún 10 restos de repetición.
Como polímeros poliamidas estructurantes lipófilos preferidos utilizables en la invención, se pueden citar las poliamidas ramificadas con cadenas grasas laterales y/o cadenas grasas terminales que tienen de 12 a 120 átomos de carbono y principalmente de 12 a 68 átomos de carbono, estando unidas las cadenas grasas terminales al esqueleto poliamida por grupos éster. Estos polímeros son más especialmente los descritos en el documento US-A5783657 de la empresa Union Camp. En particular, se pueden citar los polímeros cuyo nombre INCI es "ethylenediamine/stearyl dimer dilinoleate copolymer" y "ethylenediamine/stearyl dimer tallate copolymer ".
A título de ejemplo de polímeros estructurantes utilizables en la composición según la invención, se pueden citar los productos comerciales vendidos por la empresa Bush Boake Allen con los nombres Uniclear 80, Uniclear 100, Uniclear 80V, Uniclear 100 V y Uniclear 100 VG. Se venden respectivamente en forma de gel al 80% (en materia activa) en un aceite mineral y al 100% (en materia activa). Tienen un punto de reblandecimiento de 88 a 940C. Estos productos comerciales son una mezcla de copolímero de un diácido C36 condensado sobre etilen diamina, de masa molecular media de aproximadamente 6.000. Las terminaciones de ácido restantes están, además, esterificadas por alcohol cetílico, estearílico o sus mezclas (denominadas también alcohol cetilestearílico).
Polímeros poliureas o poliuretanos lipófilos
Como agente reológico de fase grasa, se pueden citar igualmente los poliuretanos y las poliureas solubles o dispersables en el (o los) aceite(s) hidrocarbonado(s), y que contienen:
-al menos dos grupos uretanos, o al menos dos grupos ureas o al menos un grupo uretano y un grupo urea en la cadena,
-al menos una secuencia o un injerto hidrocarbonado o poliéster alifático de cadena hidrocarbonada larga, preferentemente ramificada.
Por cadena hidrocarbonada larga, se entiende una cadena hidrocarbonada, lineal o ramificada, que contiene al menos 8 átomos de carbono y preferentemente 10 a 500 átomos de carbono.
Polímeros siliconados lipófilos:
Los agentes estructurantes lipófilos poliméricos siliconados son por ejemplo polímeros del tipo poliorganosiloxano como los descritos en los documentos US-A-5 874 069, US-A-5.919.441, US-A-6.051.216 y US-A-5.981.680. Según la invención, los polímeros utilizados como agente estructurante pueden pertenecer a las dos familias siguientes:
1) poliorganosiloxanos que contienen al menos dos grupos capaces de establecer interacciones de hidrógeno, estando situados estos dos grupos en la cadena del polímero y/o
2) poliorganosiloxanos que contienen al menos dos grupos capaces de establecer interacciones de hidrógeno, estando situados estos dos grupos en los injertos o ramificaciones.
Los grupos capaces de establecer interacciones de hidrógeno pueden elegirse entre los grupos éster, amida, sulfonamida, carbamato, tiocarbamato, urea, uretano, tiourea, oxamido, guanidino, biguanidino y sus combinaciones.
Según una primera variante, los polímeros siliconados son poliorganosiloxanos tales como los definidos anteriormente y en los que los restos capaces de establecer interacciones de hidrógeno están dispuestos en la cadena del polímero.
Según una variante de la invención, se puede utilizar también un polímero que comprende además al menos un resto hidrocarbonado que contiene dos grupos capaces de establecer interacciones de hidrógeno elegidos entre los grupos éster, amida, sulfonamida, carbamato, tiocarbamato, urea, uretano, tiourea, oxamido, guanidino, biguanidino y sus combinaciones.
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Estos copolímeros pueden ser polímeros de bloques, polímeros de secuencias o polímeros injertados.
A título de ejemplo de polímero siliconado utilizable, se puede citar una de las poliamidas siliconadas, obtenidas según los ejemplos 1 a 3 del documento US-A-5 981 680.
Según una variante de realización de la invención, el polímero está constituido por un homopolímero o copolímero que contiene grupos uretano o urea. Estos polímeros se describen con detalle en la solicitud WO 2003/106614 publicada el 24/12/2003 cuyo contenido se incorpora en la presente solicitud por referencia.
Los polímeros y copolímeros utilizados en la composición de la invención tienen ventajosamente una temperatura de transición sólido-líquido de 450C a 1900C. Preferentemente, presentan una temperatura de transición sólido-líquido que va de 70 a 1300C y mejor de 800C a 1050C.
Organogelantes:
El estructurante aceitoso puede elegirse igualmente entre los gelificantes orgánicos moleculares no poliméricos, denominados igualmente organogelantes, que son compuestos cuyas moléculas son capaces de establecer entre ellas interacciones físicas que dan lugar a una auto-agregación de las moléculas con la formación de una red supramolecular 3D que es responsable de la gelificación del (de los) aceite(s) (denominado igualmente fase grasa líquida).
La red supra-molecular puede resultar de la formación de una red de fibrillas (debidas a los apilamientos o agregaciones de moléculas de organogelante), inmovilizando las moléculas de la fase grasa líquida.
La aptitud para formar esta red de fibrillas, y por lo tanto para gelificar, depende la naturaleza (o clase química) del organogelante, de la naturaleza de los sustituyentes portados por sus moléculas para una clase química dada y de la naturaleza de la fase grasa líquida.
Las interacciones físicas son diversas pero excluyen la co-cristalización. Estas interacciones físicas son en particular interacciones del tipo interacciones de hidrógeno auto-complementarias, interacciones π entre ciclos insaturados, interacciones dipolares, uniones de coordinación con derivados organometálicos y sus asociaciones. En general, cada molécula de un organogelante puede establecer varios tipos de interacciones físicas con una molécula vecina. También, ventajosamente, las moléculas de los organogelantes según la invención contienen al menos un grupo capaz de establecer uniones de hidrógeno y mejor al menos dos grupos capaces de establecer uniones de hidrógeno, al menos un ciclo aromático y mejor al menos dos ciclos aromáticos, al menos una o varias uniones con insaturación etilénica y/o al menos uno o varios carbonos asimétricos. Preferentemente, los grupos capaces de hacer uniones de hidrógeno se eligen entre los grupos hidroxilo, carbonilo, amina, ácido carboxílico, amida, urea, bencilo y sus asociaciones.
El o los organogelantes según la invención son solubles en la fase grasa líquida después de calentamiento hasta la obtención de una fase líquida homogénea transparente. Pueden ser sólidos o líquidos a temperatura ambiente y presión atmosférica.
El o los organogelantes moleculares utilizables en la composición según la invención son principalmente los descritos en el documento "Specialist Surfactants", editado por D. Robb de 1997, p. 209-236, capítulo 8 de P. Terech, las solicitudes europeas EP-A-1068854 y EP-A-1086945 o también en la solicitud WO-A-02/47031.
Se pueden citar principalmente entre estos organogelantes, las amidas de ácidos carboxílicos en particular los ácidos tri-carboxílicos como las ciclohexanotricarboxamidas (véase la solicitud de patente europea EP-A-1068854), las diamidas que tienen cadenas hidrocarbonadas que contienen cada una de 1 a 22 átomos de carbono, por ejemplo de 6 a 18 átomos de carbono, estando dichas cadenas no sustituidas o sustituidas con al menos un sustituyente elegido entre los grupos éster, urea y flúor (véase la solicitud EP-A-1086945) y principalmente las diamidas que resultan de la reacción del diaminociclohexano, en particular del diaminociclohexano en forma trans, y de un cloruro de ácido como por ejemplo N,N'-bis (dodecanoil)-1,2-diaminociclohexano, las amidas de Nacilaminoácidos como las diamidas que resultan de la acción de un N-acilaminoácido con aminas que contienen de 1 a 22 átomos de carbono, como por ejemplo las descritas en el documento WO-93/23008 y principalmente las amidas del ácido N-acilglutámico en el que el grupo acilo representa una cadena alquilo C8 a C22 tales como dibutilamida del ácido N-lauroil-L-glutámico, fabricada o comercializada por la empresa Ajinomoto con la denominación GP-1 y sus mezclas.
Se pueden utilizar igualmente como organogelantes los compuestos de tipo bis-urea de fórmula general siguiente:
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en la que: -A es un grupo de fórmula (II): imagen13
con R1 siendo un radical alquilo C1 a C4 lineal o ramificado, y los * simbolizando los puntos de unión del grupo A a cada uno de los dos átomos de nitrógeno del resto del compuesto de fórmula general (I), y -R y R', idénticos o diferentes, se eligen entre: -i) los radicales de fórmula (III): imagen14
10 en la que:
-L es un enlace sencillo o un radical divalente carbonado, principalmente hidrocarbonado (alquileno), lineal, ramificado y/o cíclico, saturado o insaturado, que comprende 1 a 18 átomos de carbono, y que puede comprender 1 a 4 heteroátomos elegidos entre N, O y S;
-Ra es:
15 a) un radical carbonado, principalmente hidrocarbonado (alquilo), lineal, ramificado y/o cíclico, saturado o insaturado, que comprende 1 a 18 átomos de carbono, y que puede comprender 1 a 8 heteroátomos elegidos entre N, O, Si y S;
o bien b) un radical siliconado de fórmula: imagen15
20 con n estando comprendido entre 0 y 100, principalmente entre 1 y 80, incluso 2 a 20; y R2 a R6 siendo, independientemente los unos de los otros, radicales carbonados, principalmente hidrocarbonados
(alquilos), lineales o ramificados, que tienen 1 a 12, principalmente 1 a 6 átomos de carbono, y que pueden comprender 1 a 4 heteroátomos principalmente O; -Rb y Rc se eligen, independientemente el uno del otro, entre:
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a) los radicales carbonados, principalmente hidrocarbonados (alquilos), lineales, ramificados y/o cíclicos, saturados o insaturados, que comprenden 1 a 18 átomos de carbono, y que pueden comprender 1 a 4 heteroátomos elegidos entre N, O, Si y S;
b) los radicales de fórmula: imagen16
con n estando comprendido entre 0 y 100, principalmente entre 1 y 80, incluso 2 a 20; y R'2 a R'6 siendo, independientemente los unos de los otros, radicales carbonados, principalmente hidrocarbonados (alquilos), lineales o ramificados, que tienen 1 a 12, principalmente 1 a 6 átomos de carbono, y que pueden comprender 1 a 4 heteroátomos principalmente O.
10 -ii) los radicales alquilo C1 a C30, lineal, ramificado y/o cíclico, saturado o insaturado, y que comprende eventualmente 1 a 3 heteroátomos elegidos entre O, S, F y N; entendiéndose que uno al menos de los radicales R y/o R' tiene la fórmula (III). Principalmente, el grupo A puede tener la fórmula: imagen17
15 con R1 y los * siendo tales como se han definido anteriormente. En particular, R1 puede ser un grupo metilo, lo que da lugar a un grupo A de fórmula: imagen18
en la que los * son tales como se han definido anteriormente.
En particular, los compuestos según la invención pueden estar en forma de mezcla ligada al hecho de que A puede 20 ser una mezcla de 2,4-tolileno y 2,6-tolileno, principalmente en proporciones (isómero 2,4/isómero 2,6) que varían de 95/5 a 80/20.
Según la invención, uno al menos de los radicales R y/o R' debe tener la fórmula (III): imagen19
En esta fórmula, L es preferentemente un radical divalente carbonado, principalmente hidrocarbonado (alquileno), 25 lineal, ramificado y/o cíclico, saturado o insaturado, que comprende 1 a 18 átomos de carbono, y que puede
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comprender 1 a 4 heteroátomos elegidos entre N, O y S. En el radical L, la cadena carbonada puede estar interrumpida por el/los heteroátomos y/o puede comprender un sustituyente que comprende dicho/dichos heteroátomos.
En particular, L puede tener la estructura -(CH2)n-con n= 1 a 18, principalmente 2 a 12, incluso 3 a 8. Preferentemente, L se elige entre los radicales metileno, etileno, propileno, butileno y principalmente n-butileno u octileno.
El radical L puede estar igualmente ramificado, por ejemplo del tipo -(CH2)-CH(CH3)-, lo que da lugar al radical de fórmula (III) siguiente: imagen20
10 El radical Ra puede ser un radical carbonado, principalmente hidrocarbonado (alquilo), lineal, ramificado y/o cíclico, saturado o insaturado, que comprende 1 a 18 átomos de carbono, y que puede comprender 1 a 8 heteroátomos elegidos entre N, O, Si y S. La cadena carbonada puede estar interrumpida por el/los heteroátomos y/o puede comprender un sustituyente que comprende dicho/dichos heteroátomos; los heteroátomos pueden formar principalmente uno o varios grupos -SiO-(o -OSi)-.
15 Así, el radical Ra puede tener la estructura -(CH2)n'-CH3 con n'= 0 a 17, principalmente 1 a 12, incluso de 1 a 6. En particular, Ra puede ser metilo, etilo, propilo o butilo.
Puede tener igualmente la estructura -(CH2)x-O-(CH2)z-CH3 o bien -(CH2)x-O-(CH2)y-O-(CH2)z-CH3, con x= 1 a 10, preferentemente 2; y= 1 a 10 preferentemente 2, y z= 0 a 10, preferentemente 0 ó 1.
El radical Ra puede tener también la estructura -SiR4R5R6 (caso en el que n= 0), en la que R4, R5 y R6 son,
20 independientemente los unos de los otros, preferentemente, radicales alquilo, que tienen 1 a 12 átomos de carbono, principalmente 1 a 6 átomos de carbono; en particular R4, R5 y/o R6 pueden elegirse entre metilo, etilo, propilo, butilo.
El radical Ra puede ser igualmente un radical siliconado de fórmula: imagen21
25 en la que R2 a R6 son, independientemente los unos de los otros, preferentemente, radicales alquilo, que tienen 1 a 12 átomos de carbono, principalmente 1 a 6 átomos de carbono; en particular R2 a R6 pueden elegirse entre metilo, etilo, propilo, butilo;
y en particular un radical: imagen22
30 con n= 1 a 100; y más particularmente aún un radical:
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Los radicales Rb y Rc, idénticos o diferentes, pueden ser radicales carbonados, principalmente hidrocarbonados (alquilos), lineales, ramificados y/o cíclicos, saturados o insaturados, que comprenden 1 a 18 átomos de carbono, y que pueden comprender 1 a 8 heteroátomos elegidos entre N, O, Si y S, En estos radicales, la cadena carbonada
5 puede estar interrumpida por el/los heteroátomos y/o puede comprender un sustituyente que comprende dicho/dichos heteroátomos; pudiendo formar los heteroátomos principalmente uno o varios grupos -SiO-(o O-Si)-.
Así, pueden tener la estructura -(CH2)m-CH3 con m= 0 a 17, principalmente 1 a 12, incluso 2 a 5; en particular Rb y/o Rc pueden ser metilo, etilo, propilo o butilo;
Pueden tener igualmente la estructura -O-(CH2)m'-CH3 con m'= 0 a 5, principalmente 1 a 4, y en particular metoxi o 10 etoxi.
Pueden tener también la estructura -O-(CH2)x-O-(CH2)z-CH3 o -O-(CH2)x-O-(CH2)y-O-(CH2)z-CH3, con x= 1 a 10, preferentemente 2; y= 1 a 10 preferentemente 2, y z= 0 a 10, preferentemente 0 ó 1.
Pueden tener también la estructura: imagen24
15 con n estando comprendido entre 0 y 100, principalmente entre 1 y 80, incluso 2 a 20;
y siendo R'2 a R'6, independientemente los unos de los otros, preferentemente, radicales alquilo, que tienen 1 a 12 átomos de carbono, principalmente 1 a 6 átomos de carbono; en particular R'2 a R'6 puede elegirse entre metilo, etilo, propilo, butilo.
Cuando tienen la fórmula (III), los radicales R y/o R' se eligen preferentemente entre los radicales siguientes:
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e igualmente los de fórmula: imagen26
con n variando de 0 a 100 y en particular
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y imagen28
o también imagen29
en las que x = 1 a 10, preferentemente 2; e y = 1 a 10, preferentemente 2;
y siendo L tal como se ha definido anteriormente.
Preferentemente, en estas fórmulas, L es un radical alquileno C1-C8, lineal o ramificado, principalmente metileno, etileno, propileno, butileno y principalmente n-butileno, octileno o de fórmula -CH2-CH(CH3)-.
10 En un modo de realización particular, R y R', idénticos o diferentes, tienen los dos la fórmula (III).
En otro modo de realización, uno de los radicales R o R' representa un radical alquilo C1 a C30, lineal, ramificado y/o cíclico, saturado o insaturado, y comprende eventualmente 1 a 3 heteroátomos elegidos entre O, S, F y N.
Esto se ha comprobado que es particularmente ventajoso para conferir un carácter universal a los compuestos de fórmula (I), es decir les permite texturizar a la vez medios carbonados polares o apolares, medios siliconados
15 lineales o cíclicos, aceites mixtos es decir carbonados parcialmente siliconados, así como sus mezclas.
La cadena carbonada puede estar interrumpida por el/los heteroátomos y/o puede comprender un sustituyente que comprende dicho/dichos heteroátomos, principalmente en forma de grupo carbonilo (-CO-), de uno o varios radicales hidroxi (-OH), y/o de un radical éster -COOR'' con R'' = radical alquilo, lineal o ramificado, que tiene 1 a 8 átomos de carbono.
20 Así, dicho radical R o R' puede ser un grupo elegido entre:
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con * teniendo la definición proporcionada anteriormente.
En un modo de realización preferido, R o R' representa un radical alquilo ramificado, principalmente monoramificado, preferentemente no cíclico, saturado o insaturado, que comprende 3 a 16 átomos de carbono, principalmente 4 a 12, incluso 4 a 8 átomos de carbono, y que comprende eventualmente 1 a 3 heteroátomos elegidos entre O, S, F y/o N, preferentemente O y/o N.
En particular, R o R' pueden ser radicales tercio-butilo ó 2-etilhexilo o de fórmula:
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DESCRIPTION
Cosmetic process using a composition comprising siloxane resins and a powdery coloring matter
The invention relates to a cosmetic method of makeup and / or care of keratin materials comprising the application on said keratin materials, mainly the skin, lips, and preferably the skin, of a cosmetic composition, comprising siloxane resins and a powdery coloring matter treated on the surface by a hydrophobic agent. The invention relates in particular to care or makeup compositions of said keratin materials.
According to the invention, it is understood to designate by keratin matters, the skin of the body and the mucous membranes, for example the face or the lips.
It is known to use makeup products in order to add color to the skin. These products contain most of the times pigments (in particular, iron and titanium oxides) that allow a certain coverage to be obtained. Once applied to the skin, after application, this product must have good persistence properties in particular a good persistence of color, dullness, homogeneity and makeup should not be sensitive to rubbing. After the makeup, the sebum secreted by the skin over time modifies the cosmetic properties obtained from the makeup. In particular, sebum has a tendency to modify the color of makeup deposited on the skin; This modification of the color goes against the desired colored aesthetic effect, since the visual appearance of the makeup no longer corresponds to the initial color of the chosen composition. This poor persistence of makeup color throughout the day needs, therefore, to renew its application to preserve a homogeneous makeup.
To improve this persistence, polymers that provide persistence throughout the day are used. These polymers have a very different chemical nature and are transported either in a fatty phase, or in an aqueous phase (for example, silicon resins, polyacrylates, latex, etc.).
If these polymers effectively provide persistence properties, particularly non-transfer, they do not always allow color persistence throughout the day (problem of persistence of sebum and water secretion).
It is therefore necessary to find a technical solution that allows to obtain these properties of color persistence.
The objective of the present invention is therefore to propose a cosmetic procedure of care and in particular of make-up of keratin materials that allows to obtain satisfactory cosmetic properties immediately and over time, in particular that allows to obtain a persistence in time of the initial color, dullness and / or homogeneity of makeup.
This objective, as well as others, are achieved by the present invention, which mainly describes a cosmetic procedure for makeup and / or care of keratin materials comprising the application on said keratin materials, of a composition comprising, in a physiologically acceptable medium:
a) a siloxane resin comprising at least 80 mol% of units:

(i)

(R'3SiO1 / 2) to (hereinafter "M" units) and

(ii)

(SiO4 / 2) b (hereafter "Q" units)

in which
 R 'independently represents an alkyl group having 1 to 8 carbon atoms, an aryl group, a carbinol group or an amino group,
with the proviso that at least 95 mol% of the R 'groups are alkyl groups,
 a and b have values strictly above 0;
 and the a / b ratio is between 0.5 and 1.5,
b) a propyl silsesquioxane resin comprising at least 80 mol% of units (R''SiO3 / 2) (hereafter "T" units) in which R '' independently represents an alkyl group having from 1 to 8 carbon atoms, an aryl group, a carbinol group or an amino group, with the proviso that at least 80 mol% of the R groups '' are propyl groups,
the weight ratio between resins a) and b) being between 1/99 and 99/1, in particular between 85/15 and 15/85,
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the resins a) and b) not being joined to each other by covalent bonds, and the number of units M of the final mixture being strictly less than the number of units (T + Q), and c) at least one powdery dye treated on the surface by a hydrophobic agent chosen from a
compound of fluorinated nature, an amino acid, N-acylated amino acids or their salts and one of their mixtures. A subject of the present invention is also a cosmetic makeup and / or care procedure for
keratin materials comprising the application on said keratin materials, of a composition comprising, in a physiologically acceptable medium: a) a siloxane resin comprising at least 80 mol% of units:

(i)

(R'3SiO1 / 2) to (hereinafter "M" units) and

(ii)

(SiO4 / 2) b (hereafter "Q" units) in which  R 'independently represents an alkyl group having 1 to 8 carbon atoms, an aryl group, a

carbinol group or an amino group, with the proviso that at least 95 mol% of the R 'groups are alkyl groups, • a and b have values strictly greater than 0;  and the ratio a / b is between 0.5 and 1.5, b) a film-forming propyl silsesquioxane resin comprising at least 80 mol% of units (R''SiO3 / 2) (of
hereinafter "T" units) in which R '' independently represents an alkyl group having 1 to 8 carbon atoms, an aryl group, a carbinol group or an amino group, with the proviso that at least 40% In moles of the R groups '' are propyl groups,
the weight ratio between resins a) and b) between 1/99 and 99/1 being comprised, in particular between 85/15 and 15/85, resins a) and b) not being linked to each other by covalent bonds, and the number of units M of the final mixture being strictly less than the number of units (T + Q),
and c) at least one powdery coloring matter treated on the surface by a hydrophobic agent chosen from a compound of fluorinated nature, an amino acid, N-acylated amino acids or their salts and one of their mixtures.
The process according to the invention allows advantageously to obtain deposits that have a good
color persistence throughout the day, and / or a good homogeneity of makeup. The composition according to the invention can be presented in various forms, mainly in the form of powders (free or compact), of anhydrous dispersion, water / oil or water / wax emulsion, oil / water, multiple or wax / water, or also in the form of gel.
The composition according to the invention is intended in particular for makeup and / or care of the skin, lips, nails, in particular the skin.
SILOXANE RESINS
The siloxane resin a), referred to as "MQ resin" in the following, preferably comprises residual silanole groups (-SiOH). In this case, preferably the amount of -OH groups is between 2 and 10% by weight of the MQ resin, preferably between 2 and 5% by weight of the MQ resin. Preferably, the R 'groups of the MQ resin are Methyl groups.
Resin b), hereinafter referred to as "T-propyl resin" preferably comprises residual silanoles groups (-SiOH) and / or alkoxy groups. In this case, preferably the amount of -OH groups is between 2 and 10% by weight of the propyl T resin, and / or the amount of alkoxy groups is less than or equal to 20% by weight of the propyl T resin. Preferably, the amount of -OH groups is between 6 and 8% by weight of the propyl T resin, and / or the amount of alkoxy groups is less than or equal to 10% by weight of the propyl T resin.
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The propyl resin T according to the invention is such that at least 40 mol% of the R groups '' are propyl groups, preferably at least 50 mol%, and more preferably at least 90 mol%.
Covalent bond means any chemical bond between at least 2 atoms (carbon, silicon, oxygen, etc.) in which each of the attached atoms pool an electron from one of its outer layers in order to form an electron double that joins the two atoms.
The MQ resin according to the invention comprises at least 80 mol% of units:

(i)

(R'3SiO1 / 2) to (hereinafter "M" units) and

(ii)

(SiO4 / 2) b (hereafter "Q" units) in which  R 'independently represents an alkyl group having 1 to 8 carbon atoms, an aryl group, a

carbinol group or an amino group, with the proviso that at least 95 mol% of the R 'groups are alkyl groups, • a and b have values strictly greater than 0;  and the a / b ratio is between 0.5 and 1.5. The radical R 'of the MQ resin independently represents an alkyl group having 1 to 8 carbon atoms,
an aryl group, a carbinol group or an amino group.
The alkyl groups can be chosen primarily from the methyl, ethyl, propyl, butyl, pentyl, hexyl and octyl groups. Preferably, the alkyl group is a methyl or propyl group. The aryl groups can be chosen from the phenyl, naphthyl, benzyl, tolyl, xyl, xenyl, methylphenyl, 2-phenylethyl, 2 groups
phenyl-2-methylethyl, chlorophenyl, bromophenyl and fluorophenyl, the aryl group being preferably a phenyl group. In the present invention, "carbinol group" means any group containing at least one hydroxyl radical bonded to a carbon (COH). The carbinol groups may thus contain more than one COH radical, such as for example image 1
If the carbinol group is free of aryl groups, it contains at least 3 carbon atoms. If the carbinol group comprises at least one aryl group, it contains at least 6 carbon atoms.
As examples of the carbinol group free of aryl groups containing at least 3 carbon atoms, there can be mentioned the groups of formula R1OH in which R1 represents a bivalent hydrocarbon radical containing at least 3 carbon atoms or a bivalent hydrocarbonoxy radical containing At least 3 carbon atoms. As examples of group R1, there may be mentioned alkylene radicals such as - (CH2) x-, the value of x being between 3 and 10, -CH2CH (CH3) -, -CH2CH (CH3) CH2-, -CH2CH2CH ( CH2CH3) CH2CH2CH2-y -OCH (CH3) (CH2) x-the value of x being between 1 and 10.
As examples of the carbinol group containing aryl groups having at least 6 carbon atoms, there may be mentioned the groups of formula R2OH in which R2 represents an arylene radical such as - (CH2) xC6H4-, having x a value between 0 and 10, -CH2CH (CH3) (CH2) xC6H4-, having x a value between 0 and 10, - (CH2) xC6H4 (CH2) x-, having x a value between 1 and 10. The carbinol groups containing aryl groups generally contain 6 to 14 atoms.
By amino group according to the invention, groups of formula -R3NH2 or -R3NHR4NH2 are mainly understood, R3 representing a bivalent hydrocarbon radical having at least 2 carbon atoms and R4 representing a bivalent hydrocarbon radical having at least 2 carbon atoms. The R3 group generally represents an alkylene radical having 2 to 20 carbon atoms. As examples of group R3, there may be mentioned the groups ethylene, propylene, -CH2CHCH3-, butylene, -CH2CH (CH3) CH2-, pentamethylene, hexamethylene, 3-ethyl-hexamethylene, octamethylene and decamethylene.
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The group R4 generally represents an alkylene radical having from 2 to 20 carbon atoms. As examples of group R4, there may be mentioned the groups ethylene, propylene, -CH2CHCH3-, butylene, -CH2CH (CH3) CH2-, pentamethylene, hexamethylene, 3-ethyl-hexamethylene, octamethylene and decamethylene.
The amino groups are generally -CH2CH2CH2NH2 and -CH2 (CH3) CHCH2 (H) NCH3, -CH2CH2NHCH2CH2NH2, -CH2CH2NH2, -CH2CH2NHCH3, -CH2CH2CH2CH2NH2, - (CH2CH2NH) 3H and -CH2CH2N2
The MQ resins that are suitable for use as component a), as well as their manufacturing processes, are known in the state of the art. US 2 814 601, which belongs to Currie et al., Dated November 26, 1957 describes a process for manufacturing MQ resins by transforming a water-soluble silicate into a silicic acid monomer or a silicic acid oligomer using an acid . Once the appropriate polymerization has been carried out, the trimethylchlorosilane ends are introduced to obtain the MQ resin. Another process for preparing MQ resins is described in US 2 857 356 belonging to Goodwin, dated October 21, 1958. Goodwin describes a process for manufacturing an MQ resin by cohydrolysis of a mixture of an alkyl silicate and of a water-hydrolysable trialkylsilane organopolysiloxane.
The MQ resins that are suitable as component a) in the present invention may contain D and T units, with the proviso that at least 80 mol%, even 90 mol% of total siloxane units are M and Q units. The resins MQ may also contain residual hydroxy groups as mentioned hereinbefore. MQ resins may also contain supplementary ends, whereby residual hydroxy groups are reacted with appropriate M groups.
The T-propyl resin b) according to the invention comprises at least 80 mol% of units (R''SiO3 / 2) in which R '' independently represents an alkyl group having 1 to 8 carbon atoms, an aryl group , a carbinol group or an amino group, with the proviso that at least 40 mol% of the R groups '' are propyl groups.
Preferably, the propyl resin T according to the invention is such that at least 50 mol% of the R groups are propyl groups, preferably at least 90 mol%.
Preferably, the resin T propyl b) is film-forming. By "film-forming resin" is meant a resin capable of forming it alone or in the presence of an auxiliary film-forming agent, a macroscopically continuous and adherent film on keratinous materials, and preferably a cohesive film, and even better a film whose cohesion and mechanical properties are such that said film can be isolated and manipulated in isolation, for example when said film is made by coupling on a non-stick surface such as a tefloned surface
or silicone.
The definition of the radical R '' is the same as that of the radical R '. The aforementioned definitions applicable to R 'are therefore applicable to R''.
The T-propyl resin b) according to the invention is a silsesquioxane resin. Silsesquioxane resins are well known in the state of the art and are generally obtained by hydrolysis of an organosilane containing three hydrolysable groups, such as halogen or alkoxy groups, present in the molecule. The T-propyl resin b) can thus be obtained by hydrolysis of propyltrimethoxysilane, propyltriethoxysilane, propyltripropoxysilane, or by cohydrolysis of the aforementioned propylalkoxysilanes with various alkoxysilanes. As examples of these alkoxysilanes, there may be mentioned methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, dimethyldimethoxysilane and phenyltrimethoxysilane. The propyltrichlorosilane can also be hydrolyzed alone, or in the presence of alcohol. In this case, the cohydrolysis can be carried out by adding methyltrichlorosilane, dimethyldichlorosilane, phenyltrichlorosilane or similar chlorosilanes and methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane or similar methyl alkoxysilanes. As alcohols that are suitable for this purpose, there may be mentioned methanol, ethanol, n-propyl alcohol, isopropyl alcohol, butanol, methoxy ethanol, ethoxy ethanol or similar alcohols. As examples of hydrocarbon type solvents that can be used simultaneously, there may be mentioned toluene, xylene or similar aromatic hydrocarbons; hexane, heptane, isooctane or similar linear or partly branched saturated hydrocarbons; as well as cyclohexane or similar aliphatic hydrocarbons.
The T-propyl resins b) according to the invention may contain M, D and Q units, with the proviso that at least 80 mol%, even 90 mol% of the total siloxane units are T units. The propyl resins T may also contain residual hydroxy and / or alkoxy groups, as mentioned above.
The composition according to the invention also comprises a physiologically acceptable medium. By physiologically acceptable means, a medium compatible with the skin, mucous membranes and skin appendages is understood.
This medium may comprise at least one silicone or organic volatile solvent, this solvent being preferably compatible with a / and b / resins and compatible with cosmetic use. As silicon volatile solvent, there may be mentioned cyclic polysiloxanes, linear polysiloxanes and mixtures thereof.
As linear volatile polysiloxanes, there may be mentioned hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, tetradecamethylhexasiloxane and hexadecamethylheptasiloxane. As cyclic volatile polysiloxanes, there may be mentioned hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane and
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dodecamethylcyclohexasiloxane. The organic solvent may also be an alcohol such as ethanol, isopropanol, butanol, n-propanol; a ketone such as acetone, methyl ethyl ketone, or methyl isobutyl ketone; an aliphatic hydrocarbon such as heptane, hexane, octane or isododecane; a glycol ether such as propylene glycol methyl ether, dipropylene glycol methyl ether, propylene glycol n-butyl ether, propylene glycol n-propyl ether, ethylene glycol n-butyl ether.
The mixture of resins a / and b / can be obtained from each of the resins in solution in a solvent.
In general, at the end of the synthesis of the MQ resin according to the invention, this resin is obtained directly in solution in xylene.
Also, at the end of the synthesis of the T-propyl resin b) according to the invention, this resin is obtained in solution in toluene.
Each of these resins in solution is mixed with the other according to the following protocol:
1) Mix with agitation the two resin solutions, heat, mainly in a reactor or in an autoclave (to be able to operate eventually under pressure or, conversely, establishing a partial vacuum), even in an extruder equipped or not with a system of "devolatilization" of solvents, under the following specific conditions:
-heat is heated homogeneously: the heating temperature must be greater than 900C, and less than or equal to 2500C, and preferably between 900C and 1900C.
Well it can be heated to a single temperature, between 900C and 2500C,
It can be heated by successive temperature scales:
Firstly between 900C and T10C,
T10C being an intermediate temperature between 900C and T20C which is the final temperature,
for a duration between 10 minutes to 2 hours, and
between T10C and T20C, for a duration between 10 minutes to 4 hours,
the temperature T20C corresponding to the maximum temperature chosen for the reaction.
This value of T20C is variable according to the mode of operation chosen and the type of reactor chosen: classic reactor or autoclave or extruder, but T20C remains less than or equal to 2500C. Intermediate temperature scales can also be made between T10C and T20C;
-the heating duration is at least one hour in a reactor or in an autoclave and at least 10 minutes in an extruder, preferably between 1h and 5h in a reactor or in an autoclave, and preferably between 10 minutes and 2 hours in an extruder;
-with the condition that these heat treatments are made without the presence of a chemical condensation catalyst between the 2 MQ and T-propyl resins. A catalyst like this is primarily a mineral base, in particular NaOH, KOH or ammonia.
2) Optionally, after, or even during, step 1) of heat treatment of the 2 resins in the indicated temperature range, a partial or total distillation of the aromatic solvents is performed, replacing them with a cosmetically acceptable volatile solvent. A volatile solvent such as this may be primarily a volatile silicone or not, preferably decamethylcyclopentasiloxane, or a volatile organic solvent or not, preferably isododecane.
3) Optionally also, after mixing the initial 2 solutions of each resin in a volatile solvent, the mixture of the solutions is treated in a single screw or twin screw extruder type mixer with "devolatilization" in a temperature range between 900C and 2500C, which allows volatile volatile solvents to be established by establishing a partial vacuum, working continuously, and passing the molten mixture without solvent into a tap. The molten mixture is cooled at the exit of the tap and cut into solid granules or in powder form. In this case, the mixture is directly in solid form and will be re-dissolved in the solvents chosen at the time of formulation.
Also the present invention also has as its object a method that uses a composition such as that described hereinbefore comprising, in a physiologically acceptable medium:
1) the mixture between a siloxane resin a) and a propyl silsesquioxane resin b), the mixture being as described hereinbefore, and
2) at least one powdery coloring matter treated on the surface by a hydrophobic agent chosen from a compound of fluorinated nature, a fatty acid, an amino acid and one of its mixtures,
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the siloxane a) and propyl silesquioxane b) resins being formulated in the composition by a mixture capable of being obtained according to the following procedure:
 Mixing, preferably with stirring, a solution of siloxane resin with a solution of propyl silsesquioxane resin, the solvent being preferably present in each of the volatile solutions, and
 Heating, mainly in a reactor or in an autoclave or in an extruder, under the following specific conditions:
 is heated homogeneously to a temperature greater than 900C, and less than or equal to 2500C, preferably
between 900C and 1900C; heating can be done at a single temperature, or at scales of
temperature, as indicated here above;
 the heating duration is at least 1 hour in reactor or autoclave and at least 10 minutes in
extruder, preferably between 1h and 5h in reactor or autoclave and preferably between 10 minutes and 2 hours
in extruder;
 on condition that these heat treatments are carried out without the presence of a condensation catalyst
Chemistry between the 2 MQ and T propyl resins. A catalyst like this is primarily a mineral base, in
particular NaOH, KOH or ammonia.
This process may comprise, after or even during the mixing stage, a supplementary stage of partial or total distillation of the aromatic solvents, replacing them with a cosmetically acceptable volatile solvent.
In the case where an extruder is used, this process may comprise, after or even during the mixing stage, a supplementary stage of partial or total distillation of the aromatic solvents, the mixture leaving the solid state directly.
The final stage of the heat treatment, or even the heat treatment itself, can be carried out in a mixer intended for the agitation of very viscous media such as:
 a "Z-arm blender" type mixer, in particular a Brabender mixer,
 an extruder-type screw mixer, in particular a single-screw extruder or a double screw extruder (with or without a "devolatilization" stage of the starting solvents) or in an internal mixer that allows devolatilization by establishing a thin film on the walls .
The mixtures of resins 1) usable according to the invention are mainly those described in the application WO 2005/075567, in particular those described in Tables 1 and 3 of said application. Resin blends 1) described in the application WO2007 / 145765 can also be used, in particular those described in examples 12 to 14 of this application, in which the weight ratio between resins a) and b) are respectively 50 / 50, 60/40 and 71/29 (70/30).
According to a particular mode, the resin mixture 1) described in Example 1-f is used in Table 1 of the examples, in which the weight ratio between resins a) and b) is 50/50.
According to a particular mode, the resin mixture 1) described in example 22 of said application WO2005 / 075567 is used, in which the weight ratio between resins a) and b) is 85/15.
According to a particular mode, the resin mixture 1) described in example 13 of said application WO2007 / 145765 is used, in which the weight ratio between resins a) and b) is 60/40.
The weight ratio between resins a) and b) (ie a / b) is between 1/99 and 99/1, alternatively between 85/15 and 15/85.
The composition according to the invention comprises an amount of resins a) and b) of siloxane, by weight of active material (dry matter), which ranges from 0.5 to 60% by weight, based on the total weight of the composition, preferably 3 at 60% by weight, and better from 4 to 60% by weight with respect to the total weight of said composition.
According to a particular way, the amount of resins a) and b) of siloxane, by weight of active matter (dry matter) advantageously varies from 3 to 60% by weight, and better from 6 to 60% by weight with respect to the total weight of said composition. These contents are mainly adapted to compositions in anhydrous form and in particular to bar-shaped compositions, such as lipsticks.
According to another particular way, the amount of resins a) and b) of siloxane, by weight of active matter (dry matter) advantageously varies from 3 to 30% by weight, and better from 4 to 20% by weight with respect to the total weight of said composition. These contents are mainly adapted to compositions in the form of emulsions, and in particular to compositions in the form of E / H emulsions, such as liquid makeup bases.
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PULVERULENT COLORING MATERIALS TREATED ON THE SURFACE BY A HYDROPHOBIC AGENT
The powdery coloring matter treated on the surface by a hydrophobic agent can be chosen from pigments and / or pearls.
By pigments, it is necessary to understand the particles of any form, white or colored, mineral or organic, insoluble in the physiological environment, intended to color the composition.
By mother of pearl, it is necessary to understand the particles of any form, iridescent, produced mainly by certain mollusks in their shell or synthesized.
The pigments can be white or colored, mineral and / or organic. It is possible to mention, among the mineral pigments, titanium dioxide, possibly surface treated, zirconium or cerium oxides, as well as zinc, iron (black, yellow or red) or chromium oxides, the violet of manganese, ultramarine blue, chromium hydrate and ferric blue, metal powders such as aluminum powder, copper powder.
Among the organic pigments, carbon black, type D and C pigments, and cochineal barium, barium, strontium, calcium, aluminum lacquers can be mentioned.
It is also possible to cite the pigments with effect, such as particles containing an organic or mineral substrate, natural or synthetic, for example glass, acrylic resins, polyester, polyurethane, polyethylene terephthalate, ceramics or aluminas , said substrate being coated or not with metal substances such as aluminum, gold, silver, platinum, copper, bronze, or metal oxides such as titanium dioxide, iron oxide, chromium oxide and their mixtures
Pearlescent pigments may be chosen from white pearly pigments such as titanium coated mica, or bismuth oxychloride, colored pearly pigments such as titanium mica coated with iron oxides, titanium mica coated primarily with ferric blue or of chromium oxide, titanium mica coated with an organic pigment of the aforementioned type as well as pearly pigments based on bismuth oxychloride. Interferential pigments can also be used, mainly with liquid or multilayer crystals.
Coloring materials, in particular pigments treated with a hydrophobic agent, may be present in the composition in a content ranging from 0.1% to 50% by weight, based on the total weight of the composition, preferably ranging from 0, 5% to 30% by weight, and preferably ranging from 1% to 20% by weight. Powdery dye materials treated on the surface with a hydrophobic agent may constitute 10 to 100% by weight of all the dye materials.
By way of illustration of mother of pearl that can be applied in the context of the present invention, it is possible to mention mainly the mother of color or, mainly marketed by the company ENGELHARD under the name Brillant gold 212G (Timica), GoId 222C (Cloisonne), Sparkle gold (Timica), Gold 4504 (Chromalite) and Monarch gold 233X (Cloisonne); bronze mother of pearl mainly marketed by the company MERCK with the designation Bronze fine (17384) (Colorona) and Bronze (17353) (Colorona) and by the company ENGELHARD with the designation Super bronze (Cloisonne); orange pearls mainly marketed by the company ENGELHARD under the name Orange 363 C (Cloisonne) and Orange MCR 101 (Cosmica) and by the company MERCK under the name Passion orange (Colorona) and Matte orange (17449) (Microna); Brown mother of pearl mainly marketed by ENGELHARD under the designation Nu-antique copper 340XB (Cloisonne) and Brown CL4509 (Chromalite); copper-coated mother of pearl mainly marketed by ENGELHARD under the name Copper 340A (Timica); the pearls with red reflex mainly commercialized by the company MERCK with the denomination Sienna fine (17386) (Colorona); the pearls with yellow reflex mainly commercialized by the company ENGELHARD with the denomination Yellow (4502) (Chromalite); the gold-colored red pearls mainly marketed by the ENGELHARD company under the name Sunstone G012 (Gemtone); pink mother of pearl mainly marketed by the company ENGELHARD with the designation Tan opale G005 (Gemtone); black pearls with gold reflections mainly marketed by the company ENGELHARD with the designation Nu antique bronze 240 AB (Timica), blue pearls mainly marketed by the MERCK company with the designation Matte blue (17433) (Microna), white pearls with reflection silver mainly marketed by the company MERCK with the denomination Xirona Silver and the nacreres orange pink gold green mainly marketed by the company MERCK with the denomination Indian summer (Xirona) and its mixtures.
Nacreres treated on the surface by at least one hydrophobic agent may be present in the composition in a content ranging from 1 to 50% by weight, based on the total weight of the composition, better from 5 to 30% by weight.
Powdery dyes such as those described above are surface treated, totally or partially, with a hydrophobic agent: a compound of fluorinated nature, or amino acid, or N-acylated amino acid
or its salt, or one of its mixtures.
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The present invention also has as its object a composition, which can be applied in the process according to the invention, comprising, in a physiologically acceptable medium, the siloxane resins a) and b) as defined hereinbefore and at least one subject Powdery dye treated on the surface by a hydrophobic agent chosen from a compound of fluorinated nature, an amino acid, or N-acylated amino acid or its salt, and one of its mixtures.
By compound of fluorinated nature, is meant a compound comprising at least one fluorine atom.
By way of example, the hydrophobic treatment agent can be chosen from perfluoroalkyl phosphates, hexafluoropropylene polyoxides; perfluoropolyethers; the amino acids; N-acylated amino acids or their salts and mixtures thereof. Preferably, the hydrophobic treatment agent can be chosen from perfluoroalkyl phosphates, hexafluoropropylene polyoxides; perfluoropolyethers; the amino acids; N-acylated amino acids or their salts, and mixtures thereof.
Powder-treated surface-treated coloring matter can be prepared according to surface treatment techniques of chemical, electronic, mechanical-chemical or mechanical nature well known to those skilled in the art. You can also use commercial products.
The surface agent can be absorbed or adsorbed on the powdered dyes by evaporation of the solvent, chemical reaction and creation of a covalent bond.
According to one variant, the surface treatment consists of a coating of the powder coloring materials.
The coating may represent from 1 to 300% by weight of the weight of the untreated powdery dye materials, for example from 5 to 200%, in particular from 10 to 100% by weight of the weight of the untreated powdery dye materials.
The coating may represent from 0.1 to 10% by weight, and in particular from 1 to 5% by weight of the total weight of the powder coated powder.
The coating can be carried out, for example, by adsorption of a liquid surface agent on the surface of the powder coloring materials by simple mixing with stirring of the powder coloring materials and said surface agent, possibly hot, prior to the incorporation of the particles. in the other ingredients of the makeup or care composition.
The coating can be carried out, for example, by chemical reaction of a surface agent with the surface of the powder coloring materials and creation of a covalent bond between the surface agent and the powder coloring materials. This method is mainly described in US Patent 4 578 266.
The chemical surface treatment may consist of diluting the surface agent in a volatile solvent, dispersing the powdered dyes in this mixture, and slowly evaporating the volatile solvent, so that the surface agent is deposited on the surface of the materials powdery dyes.
Fluorinated surface agent
Solid particles can be surface treated totally or partially with a fluorinated compound.
Fluorinated surface agents can be chosen from perfluoroalkyl phosphates, perfluoropolyethers, polytetrafluoropolyethylene (PTFE) and perfluoroalkanes.
Perfluoropolyethers are mainly described in patent application EP-A-486135, and are sold under the trade names FOMBLIN by the company MONTEFLUOS.
Perfluoroalkyl phosphates are described in particular in JP application H05-86984. Perfluoroalkyl amine phosphate diethyl amine sold by Asahi Glass with the reference AsahiGuard AG530 can be used.
Perfluoroalkanes can be linear or cyclic perfluoroalkanes. Among the linear perfluoroalkanes, there can be mentioned the series of linear alkanes, such as perfluoroctane, perfluorononane or perfluorodecane. Among the cyclic perfluoroalkanes, there may be mentioned perfluorocycloalkanes, perfluoro (alkylcycloalkanes), perfluoropolycloalkanes, aromatic perfluorinated hydrocarbons (perfluoroarenos). Among the perfluoroalkanes, there may also be mentioned the organo-perfluorinated hydrocarbon compounds containing at least one heteroatom.
Among the perfluorocycloalkanes and perfluoro (alkylcycloalkanes) may be mentioned perfluorodecalin sold under the name "FLUTEC PP5 GMP" by the company RHODIA, perfluoro (methyldecalin), perfluoro (C3-C5 alkylcyclohexanes) such as perfluoro ( butylcyclohexane).
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Among the perfluoropolycloalkanes, bicyclo derivatives [3.3.1] nonane such as perfluorotrimethylbicyclo [3.3.1] nonane, adamantane derivatives, such as perfluorodimethylamantane, and perfluorinated derivatives of hydrogenated phenanthrene, such as tetracosafluoro, can be mentioned -tetradecahydrofenantrene.
Among the perfluoroarenos, the perfluorinated derivatives of naphthalene, such as perfluoronaphthalene and perfluoromethyl-1-naphthalene can be mentioned.
As an example of commercial references of pigments and fillers treated with a fluorinated compound, there may be mentioned:
-The yellow iron oxide / perfluoroalkyl phosphate, sold in particular under the reference PF 5 Yellow 601 by the company Daito Kasei,
-Red iron oxide / perfluoroalkyl phosphate, sold in particular with the reference PF 5 Red R 516L by the company Daito Kasei,
-The black iron oxide / perfluoroalkyl phosphate, sold in particular with the reference PF 5 Black BL 100 by the company Daito Kasei,
- Perfluoroalkyl titanium dioxide / phosphate, sold in particular with the reference PF 5 TiO2 CR 50 by the company Daito Kasei,
-The yellow iron oxide / perfluoropolymethylisopropyl ether, sold in particular with the reference Iran oxyde yellow BF-25-3 by Toshiki,
-The DC Red 7 / perfluoropolymethylisopropyl ether, sold in particular with the D&C Red 7 FHC reference by Cardre Inc.,
-The DC Red 6 / PTFE, sold in particular with the reference T 9506 by Warner -Jenkinson.
Amino acid treatment agent
The hydrophobic treatment agent can be chosen among the amino acids; N-acylated amino acids or their salts; and their mixtures.
The N-acylated amino acids may comprise an acyl group having from 8 to 22 carbon atoms, such as a 2-ethyl-hexanoyl, caproyl, lauroyl, myristoyl, palmitoyl, stearoyl, cocoyl group. The salts of these compounds may be the aluminum, magnesium, calcium, zirconium, zinc, sodium, potassium salts. The amino acid can be, for example, lysine, glutamic acid, alanine.
As an example of pigments, those sold under the commercial reference NAI -TAO-77891, NAI C33-8073 -10, NAI -C33-8075, NAI -C47-051 -10, NAI -C33-115, NAI -C33-134, NAI -C33-8001-10, NAI -C337001-10, NAI -C33-9001-10 of the company MIYOSHI KASEI.
OTHER COMPONENTS
The composition according to the invention may comprise one or more additional components, and in particular components chosen from oils, non-ionic surfactants, amphiphilic silicone elastomers, powdery dyes not treated on the surface by a hydrophobic agent, pasty compounds of origin non-animal, thickening or gelling phase rheological agents (in particular with the exception of crosslinked dimethicone polymers), waxes (in particular with the exception of candelilla wax, ozoquerite and silicone waxes), agents hydrophilic gelling agents, fillers, powdered dyes not treated on the surface by a hydrophobic agent, film-forming polymers, ionic surfactants (in particular with the exception of lauryl ether sulfate), fibers, and mixtures thereof.
In particular, the composition according to the invention may comprise one or more additional components chosen from oils, non-ionic surfactants, amphiphilic silicon elastomers, powdered dyes not treated on the surface by a hydrophobic agent, thickening or gelling rheological agents. fatty phase (in particular with the exception of crosslinked dimethicone polymers), hydrophilic gelling agents, fillers, mainly lipophilic film-forming polymers, and mixtures thereof.
Silicone elastomers
The compositions according to the invention may further comprise an amphiphilic silicone elastomer, preferably chosen from polyoxyalkylenated and polyglycerinated silicone elastomers.
As polyoxyalkylenated silicone elastomers, those described in US5236986, US5412004, US5837793, US5811487 can be cited.
As polyoxyalkylene silicone elastomers, they can be used:
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-the name INCI PEG-10 Dimethicone / Vinyl dimethicone crosspolymer: as those marketed under the names "KSG-21", "KSG-20", by Shin Etsu;
-the name INCI Lauryl PEG-15 Dimethicone / Vinyldimethicone Crosspolymer: as those marketed under the names "KSG-30" and "KSG-31", "KSG-32" (in isododecane), "KSG-33" (in trioctanoin ), "KSG-210", "KSG310" (in mineral oil), "KSG-320" (in isododecane), "KSG-330", "KSG-340" by Shin Etsu.
As polyglycerized silicone elastomers, they can be used:
-the name INCI Dimethicone (and) Dimethicone / Polyglycerin-3 crosspolymer: as marketed under the names "KSG-710" by Shin Etsu;
-the name INCI Lauryl Dimethicone / Polyglycerin-3 crosspolymer: as those marketed under the designations "KSG-840" (in Squalane) by the company Shin Etsu.
These particular elastomers, when in association with the resins according to the invention, can improve the non-transfer and comfort (flexibility) properties of the compositions comprising them.
Oils
The composition according to the invention may further comprise at least one oil.
The oil can be chosen from hydrocarbon oils, silicone oils, fluorinated oils. These oils may have animal, vegetable, mineral or synthetic origin.
The oil can be chosen from volatile oils, nonvolatile oils, and mixtures thereof.
By hydrocarbon oil, is meant an oil formed essentially, even constituted, by carbon and hydrogen atoms, and eventually oxygen, nitrogen atoms, and which does not contain silicon or fluorine atom; It may contain ester, ether, amine, amide groups.
Siliconized oil means an oil that contains at least one silicon atom, and mainly that contains Si-O groups.
Fluorinated oil means an oil that contains at least one fluorine atom.
The composition according to the invention may comprise at least one volatile oil.
By "volatile oil" is meant an oil (or non-aqueous medium) capable of evaporating in contact with the skin in less than an hour, at room temperature and atmospheric pressure. Volatile oil is a volatile cosmetic oil, liquid at room temperature, which mainly has a non-zero vapor pressure, at room temperature and atmospheric pressure, in particular that has a vapor pressure ranging from 0.13 Pa to 40,000 Pa ( 10-3 to 300 mm Hg), and preferably ranging from 1.3 Pa to 13,000 Pa (0.01 to 100 mm Hg), and preferably ranging from 1.3 Pa to
1,300 Pa (0.01 to 10 mm Hg).
In addition, volatile oil generally has a boiling point, measured at atmospheric pressure, ranging from 1500C to 2600C and preferably ranging from 1700C to 2500C.
The composition according to the invention may comprise a volatile hydrocarbon oil primarily chosen from hydrocarbon oils having a flash point ranging from 400C to 1020C, preferably ranging from 400C to 550C, and preferably ranging from 400C to 500C.
As volatile hydrocarbon oil, there can be mentioned volatile hydrocarbon oils having 8 to 16 carbon atoms and mixtures thereof, and mainly C8-C16 branched alkanes such as iso-alkanes (also called isoparaffins) C8-C16, isododecane, isodecane , isohexadecane and for example oils sold under the trade names Isopars or Permetyls, branched esters C8-C16 as iso-hexyl neopentanoate, and mixtures thereof. Preferably, the volatile hydrocarbon oil is chosen from volatile hydrocarbon oils having 8 to 16 carbon atoms and mixtures thereof, in particular between isododecane, isodecane, isohexadecane, and is mainly isododecane.
For good color persistence properties while retaining a matte and comfortable deposit for color applications, volatile hydrocarbon solvents of 8 to 16 carbon atoms, in particular 9 to 13 carbon atoms, will be preferred. As volatile solvent C8 to C16 hydrocarbon, there may be mentioned mainly linear or branched alkanes, in particular branched, such as iso-alkanes (also called isoparaffins) C8-C16, isododecane, isodecane, isohexadecane, and for example the oils sold with the trade names Isopars or Permetyls, and mixtures thereof. Preferably, the volatile hydrocarbon solvent having from 8 to 16 carbon atoms is chosen from isododecane, isodecane, isohexadecane, and their mixture.
According to a particular embodiment, the volatile solvent is isododecane.
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According to another particular embodiment, the volatile hydrocarbon solvent is a volatile linear alkane that has a flash point in the range of 70 to 1200C, and more particularly 80 to 1000C, and is mainly about 890C.
A volatile linear alkane suitable for the invention is liquid at room temperature (approximately 250C). According to one embodiment, an alkane that is suitable for the invention can be a volatile linear alkane comprising from 8 to 16 carbon atoms, in particular from 10 to 15 carbon atoms, and more particularly from 11 to 13 carbon atoms.
A volatile linear alkane that is suitable for the invention can advantageously have a plant origin.
Said alkane can be obtained, directly or in several stages, from a vegetable raw material such as an oil, a butter, a wax, etc.
By way of example of alkane which is suitable for the invention, the alkanes described in the patent application of the company Cognis WO2007 / 068371 can be mentioned.
These alkanes are obtained from fatty alcohols, themselves obtained from copra or palm oil.
As an example of a linear alkane that is suitable for the invention, there may be mentioned n-nonano (C9), n-decane (C10), nundecane (C11), n-dodecane (C12), n-tridecan (C13), n -tetradecane (C14), n-pentadecane (C15), n-hexadecane (C16) and n-heptadecane (C17), and mixtures thereof, and in particular the mixture of n-undecano (C11) and n-tridecane (C13 ) marketed under the CETIOL UT reference by the Cognis company.
According to a particular embodiment, a volatile linear alkane that is suitable for the invention can be chosen from nnonano, n-undecano, n-dodecane, n-tridecane, n-heptadecane, and mixtures thereof.
More particularly, a volatile linear alkane suitable for the invention can be applied in the form of an n-undecano / n-tridecane mixture.
Preferably, in said mixture, the n-undecano: n-tridecan weight ratio may be 50:50 to 90:10, preferably ranging from 60:40 to 80:20, preferably ranging from 65:35 to 75:25.
In particular, a composition according to the invention may comprise an n-undecane: n-tridecane mixture in a weight ratio of 70:30. This mixture is marketed under the name CETIOL UT by the company COGNIS.
For skin makeup products, mainly makeup bases and lipsticks, volatile linear hydrocarbon oils having 8 to 16 carbon atoms will be advantageously used.
As siliconized vegetable oil, there may be mentioned linear or cyclic silicones having 2 to 7 silicon atoms, these silicones possibly containing alkyl or alkoxy groups having 1 to 10 carbon atoms. As volatile silicone oil usable in the invention, there may be mentioned mainly octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, heptamethylhexyltri-siloxane, heptamethyloctyltrisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane and sustyl mixtures.
The volatile oil may be present in the composition according to the invention in a content ranging from 0.1% to 90% by weight, based on the total weight of the composition, preferably ranging from 1% to 70% by weight, and preferably ranging from 5% to 50% by weight.
The composition according to the invention may comprise at least one non-volatile oil.
By "non-volatile oil" is meant an oil that remains on the keratinous materials at room temperature and atmospheric pressure for at least several hours and which has mainly a vapor pressure of less than 10-3 mm Hg (0.13 Pa). A non-volatile oil can also be defined as having an evaporation rate such that under the conditions defined above, the amount evaporated after 30 minutes is less than 0.07 mg / cm 2.
As a non-volatile hydrocarbon oil, paraffin oil (or petrolatum), squalane, hydrogenated polyisobutylene (Parleam oil), perhydrosqualene, mink oil, turtle, soybean, sweet almond oil, calophyllum, palm oil, can be used. of grape, sesame, corn, arara, rapeseed, sunflower, cotton, apricot, castor, avocado, jojoba, olive or cereal seed seeds; esters of lanolic acid, oleic acid, lauric acid, stearic acid; fatty esters, mainly C12-C36, such as isopropyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, diisopropyl adipate, isononyl isononanoate, 2-ethyl-hexyl palmitate, 2-hexyl-decyl laurate, 2-octyl decyl palmitate, 2-octyldodecyl myristate or lactate, di (2-ethyl hexyl) succinate, diisoestearyl malate, glycerin or diglycerin triisoestearate; Behenic acid, oleic acid, linoleic acid, linolenic acid or isostearic acid; higher fatty alcohols, mainly C16-C22, such as cetanol, oleic alcohol, linoleic or linolenic alcohol, isostearic alcohol or octyl dodecanol; and their mixtures.
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In particular, to obtain a makeup that mattifies the face, keeping a comfortable use, both during application and after makeup, C6-C22 non-volatile hydrocarbon oils will be used, which can be chosen from:
-carbonates, of the following formula (I): R1-OC (= O) -O-R'1 with R1 and R'1, identical or different, representing a C4 to C12 alkyl chain, and preferably C5 to C10, linear or branched, saturated or unsaturated (preferably saturated), which eventually has at least one cycle, saturated or not, preferably saturated;
these oils of formula (I) can be dicaprilyl carbonate, marketed under the name Cetiol CC® by the company COGNIS, di (ethyl-2-hexyl) carbonate, marketed under the name TEGOSOFT DEC® by the company Goldschmidt, carbonate di-isobutyryl; di-neopentyl carbonate; dipentyl carbonate; di neoheptyl carbonate; di-heptyl carbonate; di-isononyl carbonate; or di-nonyl carbonate;
-the monoesters, of formula (II): R2-OC (= O) -R'2, with R2 and R'2, identical or different, representing a C4 to C12 alkyl chain, and preferably C5 to C10, linear or branched, saturated or unsaturated (preferably saturated), which eventually has at least one cycle, saturated or not, preferably saturated;
these oils of formula (II) may be ethyl 2-hexyl isobutyrate, ethyl 2-hexyl butyrate, capryl butyrate, isononyl isobutyrate, 2-hexyl ethyl hexanoate, isononyl hexanoate, neopentyl hexanoate, capryl heptanoate, Octyl octanoate, marketed under the name DRAGOXAT EH® by SYMRISE, isononyl isononanoate,
-the di-esters of the following formula (III): R3-OC (= O) -R'3-C (= O) -O-R''3, with R3 and R''3, identical or different, which they represent a C4 to C12 alkyl chain, and preferably C5 to C10, linear or branched, saturated or unsaturated (preferably saturated), which eventually has at least one cycle, saturated or not, preferably saturated, and R'3 represents an alkylene chain, saturated or unsaturated, C1 to C4, preferably C2 to C4, such as an alkylene chain derived from succinate (in this case R'3 is a saturated C2 alkylene chain), maleate (in this case R'3 is a C2 alkylene chain unsaturated), glutarate (in this case R'3 is a saturated C3 alkylene chain), or adipate (in this case R'3 is a saturated C4 alkylene chain); in particular R3 and R''3 are selected from isobutyl, pentyl, neopentyl, hexyl, heptyl, neoheptyl, ethyl 2-hexyl, octyl, nonyl, isononyl; preferably, dicaprilyl maleate, mainly marketed by the company ALZO; di (2-ethyl hexyl) succinate;
-the ethers, of the following formula (IV): R4-O-R4 ', with R4 and R4', identical or different, representing a C4 to C12 alkyl chain, and preferably C5 to C10, linear or branched, saturated or unsaturated (preferably saturated), which eventually has at least one cycle, saturated or not, preferably saturated; in particular R4 and R4 'are selected from isobutyl, pentyl, neopentyl, hexyl, heptyl, neoheptyl, ethyl 2-hexyl, octyl, nonyl, isononyl; Among the compounds and formula (IV), there may preferably be mentioned dicaprilyl ether, marketed under the name of Cetiol OE® by the company COGNIS;
-the tri-alkyl esters of formula (V): R5-OC (O) -CH2-CH [-OC (O) -R'5] -CH2-OC (O) -R''5, with R5, R'5 and R''5, identical or different, representing a C4-C10 alkyl chain, preferably C5-C8, linear or branched, saturated or unsaturated (preferably saturated), in particular R5, R'5 and R '' 5 are identical; preferably R5, R'5 and R''5 (in particular identical) are alkyl radicals of the following fatty acids: caprylic, ethyl-2-hexyl, neopentanoic, or neoheptanoic; one may preferably cite, as a compound of formula (V), capric caprylic triglyceride, marketed mainly under the name MYRITOL 318® by the company COGNIS;
-and their mixtures.
The non-volatile C6-C22 hydrocarbon oil advantageously used in such makeup and / or care compositions intended to mattify the face is dicaprilyl carbonate, mainly marketed under the name of CETIOL CC by the company COGNIS.
Advantageously, when the composition is intended for makeup and / or lip care and comprises a non-volatile oil, this oil is chosen from phenylated silicone oils. Said oil is also called phenylated silicone.
It is understood as phenylated silicone, an organopolysiloxane substituted with at least one phenyl group. The phenylated silicone is preferably non-volatile. By "non-volatile" is meant an oil whose vapor pressure at room temperature and atmospheric pressure is non-zero and less than 0.13 Pa.
Preferably, the molecular weight by weight of the phenylated silicone oil is between 500 and 10,000 g / mol.
The siliconized oil can be chosen from phenyl trimethicones, phenyl dimethicones, phenyl trimethylsiloxy diphenylsiloxanes, diphenyl dimethicones, diphenyl methyldiphenyl trisiloxanes, 2-phenylethyl trimethylsiloxysilicates.
Silicone oil can respond to the formula:
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wherein the R groups independently represent each other a methyl or a phenyl. Preferably in this formula, the silicone oil comprises at least three phenyl groups, for example at least four, at least five or at least six.
According to another mode of application, the silicone oil responds to the formula image3
wherein the R groups independently represent each other a methyl or a phenyl. Preferably in this formula, said organopolysiloxane comprises at least three phenyl groups, for example at least four or at least five.
10 Mixtures of the phenylated organopolysiloxanes described above may be used. Mention may be made, for example, of mixtures of triphenylated, tetra or penta-phenylated organopolysiloxane. According to another mode of application, the silicone oil responds to the formula image4
in which Me represents methyl, Ph represents phenyl. Said phenylated silicone is mainly manufactured by Dow Corning 15 with the reference Dow Corning 555 Cosmetic Fluid (INCI name: trimethyl pentaphenyl trisiloxane). The reference Dow Corning 554 Cosmetic Fluid can also be used.
According to another mode of application, the silicone oil responds to the formula image5
in which Me represents methyl, and is between 1 and 1,000, and X represents -CH2-CH (CH3) (Ph). 20 According to another mode of application, the silicone oil responds to the formula
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in which -OR 'represents -O-SiMe3, and is between 1 and 1,000 and z is between 1 and 1,000. The phenylated silicone oil may be chosen from the phenylated silicones of the following formula (VI): image7
5 in which
-R1 to R10, independently of each other, are hydrocarbon, saturated or unsaturated, linear, cyclic or branched radicals, C1-C30, -m, n, p and q are, independently of each other, integers between 0 and 900, with the
reserve that the sum "m + n + q" is different from 0.
10 Preferably, the sum "m + n + q" is between 1 and 100. Preferably, the sum "m + n + q" is between 1 and 900, even better between 1 and 800. Preferably, q is equal to 0. The phenylated silicone oil may be chosen from the phenylated silicones of the following formula (VII): image8
in which:
-R1 to R6, independently of each other, are hydrocarbon, saturated or unsaturated, linear, cyclic or branched, C1-C30,
-m, n and p are, independently of each other, integers between 0 and 100, with the proviso that the sum "n + m" is between 1 and 100.
Preferably, R1 to R6, independently of each other, represent a saturated, linear or branched hydrocarbon radical, C1-C30, mainly C1-C12, and in particular a methyl, ethyl, propyl or butyl radical.
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Mainly, R1 to R6 can be identical, and they can also be a methyl radical.
Preferably, one can have m = 1 or 2 or 3, and / on = 0 and / op = 0 or 1, in the formula (VII).
A phenylated silicone oil of formula (VI) having a viscosity at 250C between 5 and 1,500 mm2 / s (i.e. 5 to 1,500 cSt), preferably having a viscosity between 5 and 1,000 mm2 / s ( that is, 5 to 1,000 cSt).
As the phenylated silicone oil of formula (VII), mainly phenyltrimethicones such as Dow Corning DC556 (22.5 cSt), Rhône Poulenc Silbione 70663V30 oil (28 cSt), or diphenyl dimethicones such as Belsil oils can be used , mainly Belsil PDM1000 (1,000 cSt), Belsil PDM 200 (200 cSt) and Belsil PDM 20 (20 cSt) from Wacker. Values in brackets represent viscosities at 250C.
The non-volatile silicone oil can be chosen among the silicones of the formula: image9
in which:
R1, R2, R5 and R6 are, together or separately, an alkyl radical having 1 to 6 carbon atoms,
R3 and R4 are, together or separately, an alkyl radical having 1 to 6 carbon atoms, or an aryl radical,
X is an alkyl radical having 1 to 6 carbon atoms, a hydroxyl radical or a vinyl radical,
nyp being chosen so that they give the oil a molecular weight by weight less than 200,000 g / mol, preferably less than 150,000 g / mol and more preferably less than 100,000 g / mol.
The non-volatile oil may be present in a content ranging from 0.1% to 70% by weight, based on the total weight of the non-volatile liquid fatty phase, preferably ranging from 0.5% to 60% by weight, and preferably ranging from 1% to 50% by weight.
For skin makeup products, mainly makeup bases and lipsticks, volatile or non-volatile linear silicone oils will be advantageously used. The association of the resins according to the invention and of a linear siliconized oil can mainly allow to improve non-transfer.
For skin makeup products, mainly lipsticks, phenylated silicone oils will be advantageously used. The association of the resins according to the invention and of a phenylated siliconized oil can mainly allow to improve brilliance, comfort and decrease the feeling of stickiness.
Nonionic Surfactants
The composition according to the invention may comprise at least one non-ionic surfactant.
In particular, an emulsifier having an HLB equilibrium (hydrophilic-lipophilic balance) according to GRIFFIN, specific to the composition to be obtained, can be used. The HLB value according to GRIFFIN is defined in J. Soc. Cosm. Chem. 1954 (volume 5), pages 249-256. Reference can be made to the document "Encyclopedia of Chemical Technology, KIRK-OTHMER", volume 22, p. 333-432, 3rd edition, 1979. WILEY, for the definition of the properties and functions (emulsifier) of the surfactants, in particular p. 347-377 of this reference, for non-ionic surfactants.
The nonionic surfactants preferably used in the composition according to the invention are chosen from:
a) HLB non-ionic surfactants greater than or equal to 8 to 250C, used alone or in admixture; They can be cited mainly:
- the esters and ethers of bears such as the mixture of cetyl stearyl glycoside and cetyl and stearyl alcohols such as Montanov 68 from Seppic;
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- oxyethylene and / or oxypropylene ethers (which may contain from 1 to 150 oxyethylene and / or oxypropylene groups) of glycerol;
- oxyethylene and / or oxypropylene ethers (which may contain 1 to 150 oxyethylene and / or oxypropylene groups) of fatty alcohols (mainly of C8-C24 alcohol, and preferably C12-C18) such as oxyethylenated ether of cetearyl alcohol with 30 groups oxyethylenates (name CTFA "Ceteareth-30"), oxyethylene ether of stearyl alcohol with 20 oxyethylenated groups (name CTFA "Steareth-20"), and oxyethylene ether blend of fatty alcohols C12-C15 containing 7 oxyethylenated groups (name CTFA " C12-C15 Pareth-7 ") marketed under the name NEODOL 25-7® by SHELL CHEMICALS,
- fatty acid esters (mainly C8-C24 acid, and preferably C16-C22) and polyethylene glycol (which may comprise 1 to 150 ethylene glycol residues) such as PEG-50 stearate and commercialized PEG-40 monostearate with the name MYRJ 52P® by the company ICI UNIQUEMA,
- fatty acid esters (mainly C8-C24 acid, and preferably C16-C22) and oxyethylene and / or oxypropylene glycerol ethers (which may contain 1 to 150 oxyethylenated and / or oxypropylene groups), such as monostearate PEG200 glyceryl sold under the name Simulsol 220 TM® by the company SEPPIC; polyethoxylated glyceryl stearate with 30 ethylene oxide groups as the TAGAT S® product sold by the GOLDSCHMIDT company, the polyethoxylated glyceryl oleate with 30 ethylene oxide groups as the TAGAT O® product sold by the GOLDSCHMIDT company, the cocoate of polyethoxylated glyceryl with 30 ethylene oxide groups as the VARIONIC LI 13® product sold by SHEREX, the polyethoxylated glyceryl isostearate with 30 ethylene oxide groups as the TAGAT L® product sold by the GOLDSCHMIDT company and the laurate of polyethoxylated glyceryl with 30 groups of ethylene oxide as the product TAGAT I® of the company GOLDSCHMIDT.,
- fatty acid esters (mainly C8-C24 acid, and preferably C16-C22) and oxyethylene and / or oxypropylene sorbitol ethers (which may contain 1 to 150 oxyethylene and / or oxypropylene groups), such as polysorbate 20 sold under the name Tween 20® by the company CRODA, the polysorbate 60 sold under the name Tween 60® by the company CRODA,
- dimethicone copolyol, such as that sold under the name Q2-5220® by the company DOW CORNING,
- dimethicone copolyol benzoate (FINSOLV SLB 101® and 201® from FINTEX),
-propylene oxide and ethylene oxide copolymers, also referred to as OE / OP polycondensates,
-and their mixtures.
OE / OP polycondensates are more particularly copolymers consisting of polyethylene glycol and propylene glycol blocks, such as, for example, polycondensates triblock polyethylene glycol / polypropylene glycol / polyethylene glycol. These polycondensate triblocks have for example the following chemical structure: image10
formula in which a goes from 2 to 120, and b goes from 1 to 100.
The OE / OP polycondensate preferably has a weight average molecular weight ranging from 1,000 to 15,000, and better than 2,000 to 13,000. Advantageously, said OE / OP polycondensate has a turbidity temperature, at 10 g / l in distilled water, greater than or equal to 200C, preferably greater than or equal to 600C. The turbidity temperature is measured according to ISO 1065. As the polycondensate OE / OP usable according to the invention, the polycondensate triblock polyethylene glycol / polypropylene glycol / polyethylene glycol sold with the designations SYNPERONIC® as SYNPERONIC PE / L44® and SYNPERONIC can be cited PE / F127® by the company ICI.
b) non-ionic surfactants of HLB of less than 8 to 250C, possibly associated with one or more non-ionic surfactants of HLB of greater than 8 to 250C, such as those mentioned above such as:
-the esters and ethers of bears such as sucrose stearate, sucrose cocoate, sorbitan stearate and mixtures thereof as Arlatone 2121® marketed by the company ICI;
- oxyethylene and / or oxypropylene ethers (which may contain 1 to 150 oxyethylene and / or oxypropylene groups) of fatty alcohols (mainly of C8-C24 alcohol, and preferably C12-C18) such as oxyethylene ether of stearyl alcohol with 2 groups oxyethylene (CTFA name "Steareth-2");
- esters of fatty acids (mainly C8-C24 acid, and preferably C16-C22) and polyol, mainly glycerol or sorbitol, such as glyceryl stearate, glyceryl stearate such as the product sold under the name TEGIN M® by GOLDSCHMIDT, glyceryl laurate such as the product sold under the name IMWITOR 312® by HULS, polyglyceryl-2 stearate, sorbitan triestearate, glyceryl ricinoleate;
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- lecithins, such as soy lecithins (such as Emulmetik 100 J from Cargill, or Biophilic H from Lucas Meyer);
- the cyclomethicone / dimethicone copolyol mixture sold under the designation Q2-3225C® by the company DOW CORNING. The nonionic surfactant can also be chosen from a C8-C22 alkyl dimethicone copolyol, that is, a poly methyl
(C8-C22) alkyl oxypropylene and / or oxyethylene dimethyl methyl siloxane. C8-C22 alkyl dimethicone copolyol is advantageously a compound of formula (I) as follows: image11
in which:
-PE represents (-C2H4O) x- (C3H6O) and R, R being chosen from a hydrogen atom and an alkyl radical of 1 to 4 carbon atoms, going x from 0 to 100 and going y from 0 to 80, not being x and y simultaneously 0 - saying m from 1 to 40 - saying n from 10 to 200 - saying or from 1 to 100 - saying p from 7 and 21 - saying q from 0 to 4 and preferably R = H, m = 1 to 10; n = 10 to 100; o = 1 to 30; p = 15; and q = 3. As C8-C22 alkyl dimethicone copolyol, cetyl dimethicone copolyol can be cited as the product marketed
under the name Abil EM-90 by the Goldschmidt company. According to a particular mode intended to formulate stable emulsions, which have a low viscosity that allows an easy application, giving the makeup product a persistence in the makeup time once
applied, advantageously at least one siliconized non-ionic surfactant will be used, optionally associated with at least one hydrocarbon surfactant and eventually also at least one wax: As non-ionic siliconized surfactant, it can be mentioned for example: a) the polydialkyl silicones with side groups and / or polyoxyalkylene hydrophilic terminals (polyoxyethylene (or
POE) and / or polyoxypropylene (or PPO). In addition, these silicone surfactants preferably contain linear or branched C1 to C20 alkyl side groups, preferably linear alkyl groups, such as lauryl or cetyl. These surfactants can also carry organosiloxane side groups.
In particular, in this first category, one can cite:
- Polydimethyl siloxanes with POE side groups, such as mainly KF-6011, KF-6012, KF-6013, KF6015, KF-6016 and KF-6017 from Shin Etsu; - Polydimethyl siloxanes with POE side groups and with alkyl side groups, such as mainly Cetil
PEG-PPG 10/1 dimethicone, marketed under the name ABIL EM90 by Evonik
GOLDSCHMIDT; - branched polydimethylsiloxanes with POE side groups, such as mainly PEG-9 polydimethyl siloxyethyl dimethicone, marketed under the designation KF-6028 by Shin Etsu;
-the branched polydimethyl siloxanes with alkyl side groups, such as mainly lauryl PEG-9 polydimethylsiloxyethyl dimethicone, marketed under the designation KF-6038 by the company Shin Etsu.
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b) polydialkyl silicones with polyglycerol or glycerol side groups. These silicone surfactants also contain, preferably, linear or branched C1 to C20 alkyl side groups, and preferably also linear alkyl groups such as lauryl or cetyl. Also, these siliconized and glycerolated surfactants can also carry organosiloxane side groups.
In particular in this category, one can cite:
- polydimethyl siloxanes with polyglycerol side groups, such as polyglyceryl-3-dimethyloxy disiloxane, marketed under the name KF-6100 by the company Shin Etsu;
- branched polydimethyl siloxanes and with polyglycerol side groups, such as polyglyceryl-3 polydimethylsiloxyethyl dimethicone, marketed under the designation KF-6104 by Shin Etsu;
-branched polydimethyl siloxanes, with polyglycerol side groups and alkylated side groups, such as lauryl polyglyceryl -3 polydimethyl siloxyethyl dimethicone, marketed under the designation KF-6105 by Shin Etsu.
Among siliconized nonionic surfactants, Cetil PEG / PPG -10/1 dimethicone, marketed under the name ABIL EM90 by the company EVONIK GOLDSCHMIDT, is preferred.
The nonionic siliconized surfactant is advantageously in association with at least one nonionic organic surfactant.
As non-ionic organic surfactant, fatty acid esters of polyols such as mono, di, tri can be mentioned
or sesqui-oleates or sorbitol or glycerol stearates, glycerol or polyethylene glycol laurates; fatty acid esters of polyethylene glycol (monostearate or polyethylene glycol monolaurate); fatty acid esters (stearate, oleate) of polyoxyethylene sorbitol; alkyl (lauryl, cetyl, stearyl, octyl) polyoxyethylene ethers.
Among nonionic organic surfactants, it is preferred:
- polyglycerol fatty acid esters containing at least 3 glycerol ether moieties, such as polyglyceryl 3;
-the esters of polyoxyalkylenated fatty acids (polyoxyethylene and / or polyoxypropylene), preferably containing at least 3 oxyethylene groups;
- ethers of fatty alcohols and polyglycerols with at least 3 glyceryl ether moieties;
-the ethers of fatty alcohols and polyoxyalkylene (POE and / or POE / PPO) with at least 3 POE groups.
Among the non-ionic organic surfactants, polyglyceryl-4-isostearate marketed under the name ISOLAN GI34® by the company EVONIK GOLDSCHMIDT is preferred.
In association with the non-ionic siliconized surfactant and the non-ionic organic surfactant, at least one wax may be advantageously used.
Among the waxes, the mixture of ethylene glycol acetyl / glyceryl tri-stearate, mainly marketed under the name UNITWIX by the company UNITED GARDIAN, is preferred.
Thickening or gelling phase rheological agent
The composition according to the invention may further comprise a rheological thickening agent or fat phase gelling agent.
"Thickening rheological agent or fat phase gelling agent" means a compound capable of increasing the viscosity of the fatty phase of the composition. The rheological thickening or gelling agent of the fatty phase allows mainly to obtain a composition that can have a texture ranging from fluid to solid textures.
Preferably, the fatty phase thickening or gelling rheological agents are chosen from the crystalline polymers, lipophilic mineral structuring agents, lipophilic polyamides, lipophilic polyureas and polyurethanes, siliconized polymers comprising, where appropriate, at least one hydrocarbon moiety containing two groups capable of establishing hydrogen interactions chosen from the groups ester, amide, sulfonamide, carbamate, thiocarbamate, urea, urethane, thiourea, oxamido, guanidino, biguanidino and their combinations, organogelants, block polymers, cholesteric liquid crystal agents, dimethicone / vinyl dimethicone copolymers, and vinyl dimethicone / alkyl dimethicone copolymers, such as vinyl dimethicone / lauryl dimethicone copolymers.
The thickening or gelling phase rheological agent can be chosen from:
-crystalline polymers, preferably chosen from semi-crystalline polymers, dextrin and fatty acid esters, hydrophobic modified polysaccharides, copolymers of crystalline olefins and crystalline polycondensates;
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- mineral lipophilic structuring agents, such as lipophilic clays and hydrophobic silicas, such as hydrophobic treated pyrogenated silica,
-Lipophilic polyamide type polymers,
-polyureas and lipophilic polyurethanes,
-the siliconized polymers, where appropriate, include at least one hydrocarbon moiety containing two groups capable of establishing hydrogen interactions chosen from the ester, amide, sulfonamide, carbamate, thiocarbamate, urea, urethane, thiourea, oxamido, guanidino, biguanidino and their combinations, preferably amide groups,
-the organogelants;
-block polymers;
-the agents of cholesteric liquid crystals;
-the silicone elastomers;
-and their mixtures.
Preferably, the fatty phase rheological agent is chosen from semi-crystalline polymers, block polymers, lipophilic polyamide polymers, and siliconized polymers comprising at least one hydrocarbon moiety containing two groups capable of establishing hydrogen interactions chosen from the amide groups, lipophilic mineral structuring agents, in particular lipophilic clays and hydrophobic silicas, and silicone elastomers.
It is specified that, according to the invention, in the case of the associations of a rheological agent of the fatty phase with an oil, "oil" means a liquid fatty body at room temperature. The oils can be those described above.
Structuring agents lipophilic minerals
The thickening or gelling phase rheological agent may be a lipophilic mineral structuring agent.
Mention may be made of lipophilic clays, such as possibly modified clays such as hectorites modified by a C10 to C22 fatty acid ammonium chloride, as a hectorite modified by di-stearyl di-methyl ammonium chloride.
Clays are silicates that contain a cation that can be chosen from calcium, magnesium, aluminum, sodium, potassium, lithium cations, and mixtures thereof.
By way of examples of such products, clays of the smectite family such as montmorillonites, hectorites, bentonites, beidelites, saponites, as well as the family of vermiculites, stevensite, chlorites can be mentioned. These clays can have natural or synthetic origin.
The clay can be chosen from montmorillonite, bentonite, hectorite, attapulgite, sepiolite, and mixtures thereof. The clay is preferably a bentonite or a hectorite.
Organophilic clays are modified clays with a chemical compound chosen from quaternary amines, tertiary amines, aminated acetates, imidazolines, aminated soaps, fatty sulfates, alkyl aryl sulphonates, amine oxides, and mixtures thereof.
As organophilic clays, there may be mentioned quaternium-18 bentonites such as those sold under the denominations Bentone 3, Bentone 38, Bentone 38V by the Elementis company, Tixogel VP by the United catalyst company, Claytone 34, Claytone 40, Claytone XL by the Southern Clay company; Bentonite stearalkonium such as those sold under the names Bentone 27V by Elementis, Tixogel LG by United Catalyst, Claytone AF, Claytone APA by Southern Clay; quaternium-18 / benzalkonium bentonite such as those sold under the Claytone HT designations, Claytone PS by the Southern Clay company.
According to a preferred embodiment, the thickening agent is chosen from the organophilic modified clays, such as benzyl dimethyl ammonium stearate modified hectorite.
Hydrophobic silicas can also be mentioned, such as surface-treated hydrophobic pyrogenated silica, whose particle size is less than 1 μm. It is indeed possible to chemically modify the surface of the silica, by chemical reaction that generates a decrease in the number of silanol groups present on the surface of the silica. Silanol groups can be substituted mainly by hydrophobic groups: a hydrophobic silica is obtained. Hydrophobic groups can be:
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-trimethylsiloxyl groups, which are mainly obtained by treating pyrogenated silica in the presence of hexamethyldisilazane. Silicas thus treated are called "Silica silylate" according to CTFA (6th edition, 1995). They are marketed, for example, with the references "AEROSIL R812®" by Degussa, "CAB-O-SIL TS-530®" by Cabot.
-dimethylsilyloxy or polydimethylsiloxane groups, which are mainly obtained by treatment of pyrogenated silica in the presence of polydimethylsiloxane or dimethyldichlorosilane. Silicas thus treated are called "Silica dimethyl silylate" according to CTFA (6th edition, 1995). They are marketed, for example, with the references "AEROSIL R972®", "AEROSIL R974®" by Degussa, "CAB-O-SIL TS-610®", "CAB-O-SIL TS-720®" by Cabot company.
The hydrophobic pyrogenated silica preferably has a particle size that can be nanometric to micrometric, for example, ranging from about 5 to 200 nm.
Lipophilic polyamide polymers
By polymer, in the sense of the invention is meant a compound having at least 2 repeat residues, preferably at least 3 repetition residues and even better 10 repetition residues.
As preferred lipophilic structuring polyamide polymers usable in the invention, there may be mentioned branched polyamides with side fatty chains and / or terminal fatty chains having 12 to 120 carbon atoms and mainly 12 to 68 carbon atoms, the chains being joined terminal fats to the polyamide skeleton by ester groups. These polymers are more especially those described in US-A5783657 of the company Union Camp. In particular, polymers whose INCI name is "ethylenediamine / stearyl dimer dilinoleate copolymer" and "ethylenediamine / stearyl dimer tallate copolymer" may be mentioned.
As an example of structuring polymers usable in the composition according to the invention, commercial products sold by the Bush Boake Allen company with the names Uniclear 80, Uniclear 100, Uniclear 80V, Uniclear 100 V and Uniclear 100 VG can be cited. They are sold respectively in the form of 80% gel (in active matter) in a mineral oil and 100% (in active matter). They have a softening point of 88 to 940C. These commercial products are a mixture of copolymer of a C36 diacid condensed on ethylene diamine, of average molecular mass of approximately 6,000. The remaining acid terminations are also esterified by cetyl, stearyl alcohol or mixtures thereof (also called cetyl stearyl alcohol).
Polyurea polymers or lipophilic polyurethanes
As the rheological agent of the fatty phase, there may also be mentioned polyurethanes and polyureas soluble or dispersible in the hydrocarbon oil (s), and containing:
- at least two urethane groups, or at least two ureas groups or at least one urethane group and one urea group in the chain,
- at least one sequence or a hydrocarbon graft or aliphatic long chain hydrocarbon polyester, preferably branched.
By "long hydrocarbon chain" is meant a hydrocarbon chain, linear or branched, containing at least 8 carbon atoms and preferably 10 to 500 carbon atoms.
Silicophilic lipophilic polymers:
Silicone polymeric lipophilic structuring agents are for example polymers of the polyorganosiloxane type such as those described in US-A-5 874 069, US-A-5,919,441, US-A-6,051,216 and US-A-5,981,680 . According to the invention, the polymers used as a structuring agent can belong to the following two families:
1) polyorganosiloxanes containing at least two groups capable of establishing hydrogen interactions, these two groups being located in the polymer chain and / or
2) polyorganosiloxanes containing at least two groups capable of establishing hydrogen interactions, these two groups being located in the grafts or branches.
The groups capable of establishing hydrogen interactions can be selected from the groups ester, amide, sulfonamide, carbamate, thiocarbamate, urea, urethane, thiourea, oxamido, guanidino, biguanidino and combinations thereof.
According to a first variant, the siliconized polymers are polyorganosiloxanes such as those defined above and in which the moieties capable of establishing hydrogen interactions are arranged in the polymer chain.
According to a variant of the invention, a polymer can also be used which also comprises at least one hydrocarbon moiety containing two groups capable of establishing hydrogen interactions selected from the ester, amide, sulfonamide, carbamate, thiocarbamate, urea, urethane, thiourea groups. , oxamido, guanidino, biguanidino and their combinations.
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These copolymers can be block polymers, sequence polymers or grafted polymers.
As an example of a usable silicone polymer, one of the silicone polyamides, obtained according to examples 1 to 3 of US-A-5 981 680, can be cited.
According to a variant embodiment of the invention, the polymer is constituted by a homopolymer or copolymer containing urethane or urea groups. These polymers are described in detail in the application WO 2003/106614 published on 12/24/2003 whose content is incorporated in the present application by reference.
The polymers and copolymers used in the composition of the invention advantageously have a solid-liquid transition temperature of 450C to 1900C. Preferably, they have a solid-liquid transition temperature ranging from 70 to 1300C and better from 800C to 1050C.
Organogelants:
The oily structuring agent can also be chosen among non-polymeric molecular organic gelling agents, also called organogelants, which are compounds whose molecules are capable of establishing between them physical interactions that give rise to a self-aggregation of the molecules with the formation of a 3D supramolecular network. which is responsible for the gelation of the oil (s) (also called liquid fat phase).
The supra-molecular network can result from the formation of a network of fibrils (due to stacks or aggregations of organogelant molecules), immobilizing the molecules of the liquid fatty phase.
The ability to form this network of fibrils, and therefore to gel, depends on the nature (or chemical class) of the organogelant, on the nature of the substituents carried by their molecules for a given chemical class and on the nature of the fatty phase. liquid
Physical interactions are diverse but exclude co-crystallization. These physical interactions are, in particular, self-complementary hydrogen interactions, π interactions between unsaturated cycles, dipole interactions, coordination junctions with organometallic derivatives and their associations. In general, each molecule of an organogelant can establish various types of physical interactions with a neighboring molecule. Also, advantageously, the molecules of the organogelants according to the invention contain at least one group capable of establishing hydrogen bonds and better at least two groups capable of establishing hydrogen bonds, at least one aromatic cycle and better at least two aromatic cycles, at at least one or more joints with ethylenic unsaturation and / or at least one or more asymmetric carbons. Preferably, the groups capable of making hydrogen bonds are chosen from the hydroxyl, carbonyl, amine, carboxylic acid, amide, urea, benzyl groups and their associations.
The organogelants according to the invention are soluble in the liquid fatty phase after heating until a transparent homogeneous liquid phase is obtained. They can be solids or liquids at room temperature and atmospheric pressure.
The molecular organogelants usable in the composition according to the invention are mainly those described in the "Specialist Surfactants" document, edited by D. Robb of 1997, p. 209-236, chapter 8 of P. Terech, European applications EP-A-1068854 and EP-A-1086945 or also in application WO-A-02/47031.
Among these organogelants, the carboxylic acid amides, in particular tri-carboxylic acids such as cyclohexanedricarboxamides (see European patent application EP-A-1068854), diamides having hydrocarbon chains containing each of 1 to 22 carbon atoms, for example from 6 to 18 carbon atoms, said chains being unsubstituted or substituted with at least one substituent selected from the ester, urea and fluorine groups (see application EP-A-1086945) and mainly the diamides resulting from the reaction of diaminocyclohexane, in particular of diaminocyclohexane in trans form, and of an acid chloride such as, for example, N, N'-bis (dodecanoyl) -1,2-diaminocyclohexane, the nazylamino acid amides such as the resulting diamides of the action of an N-acylamino acid with amines containing 1 to 22 carbon atoms, such as those described in WO-93/23008 and mainly ami das of the N-acylglutamic acid in which the acyl group represents a C8 to C22 alkyl chain such as N-lauroyl-L-glutamic acid dibutylamide, manufactured or sold by the company Ajinomoto under the designation GP-1 and mixtures thereof.
The bis-urea type compounds of the following general formula can also be used as organogelants:
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in which: -A is a group of formula (II): image13
with R1 being a linear or branched C1 to C4 alkyl radical, and * symbolizing the points of attachment of group A to each of the two nitrogen atoms of the remainder of the compound of general formula (I), and -R and R ' , identical or different, are chosen from: -i) the radicals of formula (III): image14
10 in which:
-L is a single bond or a divalent carbon radical, mainly hydrocarbon (alkylene), linear, branched and / or cyclic, saturated or unsaturated, comprising 1 to 18 carbon atoms, and which may comprise 1 to 4 heteroatoms chosen from N , O and S;
-Ra is:
15 a) a carbon radical, mainly hydrocarbon (alkyl), linear, branched and / or cyclic, saturated or unsaturated, comprising 1 to 18 carbon atoms, and which may comprise 1 to 8 heteroatoms chosen from N, O, Si and S;
or b) a siliconized radical of the formula: image15
20 with n being between 0 and 100, mainly between 1 and 80, even 2 to 20; and R2 to R6 being, independently of each other, carbon radicals, mainly hydrocarbons
(alkyls), linear or branched, having 1 to 12, mainly 1 to 6 carbon atoms, and which may comprise 1 to 4 heteroatoms, mainly O; -Rb and Rc are chosen, independently of each other, between:
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a) carbon radicals, mainly hydrocarbons (alkyls), linear, branched and / or cyclic, saturated or unsaturated, comprising 1 to 18 carbon atoms, and which may comprise 1 to 4 heteroatoms chosen from N, O, Si and S ;
b) the radicals of formula: image16
with n being between 0 and 100, mainly between 1 and 80, even 2 to 20; and R'2 to R'6 being, independently of each other, carbon radicals, mainly hydrocarbons (alkyls), linear or branched, having 1 to 12, mainly 1 to 6 carbon atoms, and which may comprise 1 to 4 heteroatoms mainly O.
10 -ii) C1 to C30 alkyl radicals, linear, branched and / or cyclic, saturated or unsaturated, and possibly comprising 1 to 3 heteroatoms chosen from O, S, F and N; it being understood that at least one of the radicals R and / or R 'has the formula (III). Mainly, group A can have the formula: image17
15 with R1 and the * being as defined above. In particular, R1 can be a methyl group, which results in a group A of formula: image18
in which the * are as defined above.
In particular, the compounds according to the invention may be in the form of a mixture linked to the fact that A may be a mixture of 2,4-tolylene and 2,6-tolylene, mainly in proportions (2,4-isomer / 2-isomer, 6) that vary from 95/5 to 80/20.
According to the invention, at least one of the radicals R and / or R 'must have the formula (III): image19
In this formula, L is preferably a divalent carbon radical, mainly hydrocarbon (alkylene), linear, branched and / or cyclic, saturated or unsaturated, comprising 1 to 18 carbon atoms, and which can
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comprising 1 to 4 heteroatoms chosen from N, O and S. In the radical L, the carbon chain may be interrupted by the heteroatoms and / or may comprise a substituent comprising said / said heteroatoms.
In particular, L can have the structure - (CH2) n-with n = 1 to 18, mainly 2 to 12, even 3 to 8. Preferably, L is chosen from the radicals methylene, ethylene, propylene, butylene and mainly n- butylene or octylene.
The radical L can also be branched, for example of the type - (CH2) -CH (CH3) -, which gives rise to the radical of formula (III) as follows: image20
The radical Ra may be a carbon radical, mainly hydrocarbon (alkyl), linear, branched and / or cyclic, saturated or unsaturated, comprising 1 to 18 carbon atoms, and which may comprise 1 to 8 heteroatoms chosen from N, O , Si and S. The carbon chain may be interrupted by the heteroatom (s) and / or may comprise a substituent comprising said / said heteroatoms; the heteroatoms can mainly form one or more groups -SiO- (or -OSi) -.
Thus, the radical Ra can have the structure - (CH2) n'-CH3 with n '= 0 to 17, mainly 1 to 12, even 1 to 6. In particular, Ra can be methyl, ethyl, propyl or butyl .
It may also have the structure - (CH2) xO- (CH2) z-CH3 or - (CH2) xO- (CH2) yO- (CH2) z-CH3, with x = 1 to 10, preferably 2; y = 1 to 10 preferably 2, and z = 0 to 10, preferably 0 or 1.
The radical Ra can also have the structure -SiR4R5R6 (in which case n = 0), in which R4, R5 and R6 are,
20 independently of one another, preferably alkyl radicals, having 1 to 12 carbon atoms, mainly 1 to 6 carbon atoms; in particular R4, R5 and / or R6 can be chosen from methyl, ethyl, propyl, butyl.
The radical Ra can also be a siliconized radical of the formula: image21
Wherein R2 to R6 are, independently of each other, preferably alkyl radicals, having 1 to 12 carbon atoms, mainly 1 to 6 carbon atoms; in particular R2 to R6 can be chosen from methyl, ethyl, propyl, butyl;
and in particular a radical: image22
30 with n = 1 to 100; and more particularly still a radical:
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The radicals Rb and Rc, identical or different, may be carbon radicals, mainly hydrocarbons (alkyls), linear, branched and / or cyclic, saturated or unsaturated, comprising 1 to 18 carbon atoms, and which may comprise 1 to 8 heteroatoms chosen from N, O, Si and S, In these radicals, the carbon chain
5 may be interrupted by the heteroatom (s) and / or may comprise a substituent comprising said / said heteroatoms; the heteroatoms being able to form mainly one or several groups -SiO- (or O-Si) -.
Thus, they can have the structure - (CH2) m-CH3 with m = 0 to 17, mainly 1 to 12, even 2 to 5; in particular Rb and / or Rc can be methyl, ethyl, propyl or butyl;
They can also have the structure -O- (CH2) m'-CH3 with m '= 0 to 5, mainly 1 to 4, and in particular methoxy or ethoxy.
They can also have the structure -O- (CH2) xO- (CH2) z-CH3 or -O- (CH2) xO- (CH2) and O- (CH2) z-CH3, with x = 1 to 10, preferably 2; y = 1 to 10 preferably 2, and z = 0 to 10, preferably 0 or 1.
They can also have the structure: image24
15 with n being between 0 and 100, mainly between 1 and 80, even 2 to 20;
and R'2 to R'6 being, independently of each other, preferably alkyl radicals, having 1 to 12 carbon atoms, mainly 1 to 6 carbon atoms; in particular R'2 to R'6 can be chosen from methyl, ethyl, propyl, butyl.
When they have the formula (III), the radicals R and / or R 'are preferably chosen from the following radicals:
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and also those of formula: image26
with n varying from 0 to 100 and in particular
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Y image28
or also image29
in which x = 1 to 10, preferably 2; ey = 1 to 10, preferably 2;
and where L is as defined above.
Preferably, in these formulas, L is a linear or branched C1-C8 alkylene radical, mainly methylene, ethylene, propylene, butylene and mainly n-butylene, octylene or of the formula -CH2-CH (CH3) -.
In a particular embodiment, R and R ', identical or different, both have the formula (III).
In another embodiment, one of the radicals R or R 'represents a C1 to C30 alkyl radical, linear, branched and / or cyclic, saturated or unsaturated, and optionally comprises 1 to 3 heteroatoms chosen from O, S, F and N .
This has been found to be particularly advantageous in conferring a universal character to the compounds of formula (I), that is to say, allows them to texturize polar or apolar carbon media, siliconized media at the same time.
15 linear or cyclic, mixed oils ie partially siliconized carbonates, as well as their mixtures.
The carbon chain may be interrupted by the heteroatoms and / or may comprise a substituent comprising said / said heteroatoms, mainly in the form of a carbonyl group (-CO-), of one or more hydroxy radicals (-OH), and / or of an ester radical -COOR "with R" = alkyl radical, linear or branched, having 1 to 8 carbon atoms.
20 Thus, said radical R or R 'can be a group chosen from:
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with * having the definition provided above.
In a preferred embodiment, R or R 'represents a branched alkyl radical, mainly monobranched, preferably non-cyclic, saturated or unsaturated, comprising 3 to 16 carbon atoms, mainly 4 to 12, even 4 to 8 carbon atoms, and possibly comprising 1 to 3 heteroatoms chosen from O, S, F and / or N, preferably O and / or N.
In particular, R or R 'may be third-butyl or 2-ethylhexyl radicals or of the formula:

o un grupo hidrocarbonado alifático insaturado que comprende de 2 a 10, preferentemente de 3 a 5 átomos de carbono como por ejemplo un grupo vinilo o un grupo -R''-CH=-CHR''' en el que R'' es una cadena hidrocarbonada alifática divalente, que comprende de 1 a 8 átomos de carbono, unida al átomo de silicio y R''' es un átomo de hidrógeno o un radical alquilo que comprende de 1 a 4 átomos de carbono, preferentemente un átomo de hidrógeno; se pueden citar como grupo R' los grupos vinilo, alilo y sus mezclas; o

o un grupo hidrocarbonado cíclico insaturado que comprende de 5 a 8 átomos de carbono como por ejemplo un grupo ciclohexenilo.

Preferentemente R' es un grupo hidrocarbonado alifático insaturado, preferentemente un grupo vinilo.
Según un modo de realización, R representa un radical alquilo que comprende de 1 a 10 átomos de carbono o también un grupo fenilo, y preferentemente un radical metilo, y R' es un grupo vinilo.
El compuesto Y puede elegirse ventajosamente entre los poliorganosiloxanos que comprenden al menos una unidad alquilhidrógenosiloxano de fórmula siguiente; imagen55
en la que:
R representa un grupo hidrocarbonado monovalente, lineal o cíclico, que comprende de 1 a 30 átomos de carbono, como por ejemplo un radical alquilo que tiene de 1 a 30 átomos de carbono, preferentemente de 1 a 20 y mejor de 1 a 10 átomos de carbono, en particular un radical metilo, o también un grupo fenilo y p es igual a 1 ó 2. Preferentemente, R es un grupo hidrocarbonado, preferentemente metilo.
Según un modo de realización, las composiciones que comprenden el compuesto X y/o Y pueden comprender además un compuesto reactivo adicional tales como:
-las partículas orgánicas o minerales que comprenden en su superficie al menos 2 grupos alifáticos insaturados, se pueden citar por ejemplo las sílices tratadas en superficie por ejemplo por compuestos siliconados con grupos vinílicos tales como por ejemplo la sílice tratada ciclotetrametiltetravinilsiloxano,
-compuestos silazanos tales como hexametildisilazano.
La reacción de hidrosililación se hace en presencia de un catalizador que pude estar presente con uno u otro de los compuestos X o Y o estar presente de manera aislada. Por ejemplo, este catalizador puede estar presente en la composición en una forma encapsulada si los dos compuestos X e Y, cuando debe provocar la interacción, están presentes en esta misma composición en una forma no encapsulada o a la inversa puede estar presente en una forma no encapsulada si al menos uno de los compuestos X e Y está presente en la composición en una forma encapsulada. El catalizador es preferentemente a base de platino o de estaño.
El catalizador puede estar presente en un contenido que va de 0,0001% a 20% en peso respecto al peso total de la composición que lo comprende.
Los compuestos X y/o Y pueden estar asociados con inhibidores o retardantes de la polimerización, y más particularmente inhibidores del catalizador. De forma no limitativa, se pueden citar los polimetilvinilsiloxanos cíclicos, y en particular el tetravinil tetrametil ciclotetrasiloxano, alcoholes acetilénicos, preferentemente volátiles, tales como metilisobutinol.
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La presencia de sales iónicas, tales como acetato de sodio, puede tener una influencia en la velocidad de polimerización de los compuestos.
A título de ejemplo de una combinación de compuestos X e Y que reaccionan por hidrosililación en presencia de un catalizador, se pueden citar las referencias siguientes propuestas por la empresa Dow Corning: DC 7-9800 Soft Skin Adhesive Partes A y B, así como la combinación de mezclas A y B siguientes preparadas por Dow Corning:
MEZCLA A:

Ingrediente (Nombre INCI)

Nº CAS Contenidos (%) Función

Dimethyl Siloxane, Dimethylvinylsiloxyterminales

68083-19-2 55-95 Polímero

Silica Silycate

68909-20-6 10-40 Carga

1,3-Diethenyl-1,1,3,3-Tetramethyldisiloxane complejos

68478-92-2 Traza Catalizador

Tetramethyldivinyldisiloxane

2627-95-4 0,1-1 Polímero

MEZCLA B:

Ingrediente (Nombre INCI)

Nº CAS Contenidos (%) Función

Dimethyl Siloxane, Dimethylvinylsiloxyterminales

68083-19-2 55-95 Polímero

Silica Silycate

68909-20-6 10-40 Carga

Dimethyl, Methylhydrogen Siloxane, trimethylsiloxyterminales

68037-59-2 1-10 Polímero

10 El compuesto X puede representar de 0,1% a 95% en peso respecto al peso total de la composición que lo contiene, preferentemente de 1% a 90%, y mejor de 5% a 80%.
El compuesto Y puede representar de 0,1% a 95% en peso respecto al peso total de la composición que lo contiene, preferentemente de 1% a 90%, y mejor de 5% a 80%.
La composición según la invención puede comprender un agente plastificante que favorece la formación de una 15 película con el polímero filmógeno. Dicho agente plastificante puede elegirse entre todos los compuestos conocidos por el experto en la técnica como que son susceptibles de cumplir la función buscada.
Tensioactivos iónicos
Las composiciones según la invención pueden comprender además al menos un tensioactivo iónico.
El tensioactivo puede ser lipófilo y/o hidrófilo, utilizado solo o en acoplamiento. El tensioactivo puede elegirse entre 20 los tensioactivos aniónicos, catiónicos, anfóteros.
El tensioactivo puede estar presente en la composición según la invención en un contenido que va de 0,1% a 10% en peso, respecto al peso total de la composición, y preferentemente va de 0,5% a 8% en peso, y preferentemente va de 0,5% a 7% en peso.
Preferentemente, los tensioactivos iónicos se eligen entre los tensioactivos catiónicos, tensioactivos anfóteros,
25 carboxilatos, tauratos y N-acil N-metiltauratos, alquilsulfoacetatos, polipéptidos, derivados aniónicos de alquil poliglicósido, sales de ácidos grasos C16-C30 que derivan de aminas, sales de ácidos grasos polioxietilenados, ésteres fosfóricos y sus sales, sulfosuccinatos, alquil sulfatos, isetionatos y N-acilisetionatos, acilglutamatos, derivados de soja, citratos, derivados de prolina, lactilatos, sarcosinatos, sulfonatos y glicinatos.
Cuando el tensioactivo iónico es un tensioactivo aniónico, se elige entre:
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-carboxilatos, como 2-(2-Hidroxialquiloxi) acetato de sodio; -tauratos y N-acil N-metiltauratos; -alquilsulfoacetatos; -polipéptidos; -derivados aniónicos de alquil poliglicósido (acil-D-galactósido uronato); -sales de ácidos grasos C16-C30 principalmente las que derivan de aminas, como estearato de trietanolamina y/o
estearato de amino-2-metil-2-propano di-ol-1,3; -sales de ácidos grasos polioxietilenados principalmente las que derivan de aminas o sales alcalinas, y sus mezclas; -ésteres fosfóricos y sus sales tales como "DEA oleth-10 phosphate" (Crodafos N 10N de la empresa CRODA) o
fosfato de monocetilo monopotásico (Amphisol K de Givaudan);
-sulfosuccinatos tales como "Disodium PEG-5 citrate lauryl sulfosuccinate" y "Disodium ricinoleamido MEA sulfosuccinate"; -alquil sulfatos; -isetionatos y N-acilisetionatos; -acilglutamatos tales como "Disodium hydrogenated tallow glutamate" (AMISOFT HS-21 R® comercializado por la
empresa AJINOMOTO) y estearoil glutamato de sodio (AMISOFT HS-11 PF® comercializado por la empresa AJINOMOTO) y sus mezclas; -derivados de soja como soyato de potasio;
-citratos, como Citrato de gliceril estearato (Axol C 62 Pellets de Degussa); -derivados de prolina, como Palmitoil prolina sódica (Sepicalm VG de Seppic), o la Mezcla de Palmitoil sarcosinato sódico, Palmitoil glutamato de magnesio, Ácido palmítico y Palmitoil prolina (Sepifeel One de Seppic);
-lactilatos, como Estearoil lactilato de sodio (Akoline SL de Karlshamns AB);
-sarcosinatos, como palmitoil sarcosinato sódico (Nikkol sarcosinate PN) o la mezcla de Estearoil sarcosina y Miristoil sarcosina 75/25 (Crodasin SM de Croda); -sulfonatos, como Alquil C14-17 sec sulfonato de sodio (Hostapur SAS 60 de Clariant); -glicinatos, como cocoil glicinato de sodio (Amilite GCS-12 de Ajinomoto). Las composiciones según la invención pueden contener igualmente uno o varios tensioactivos anfotéricos como N
acil-aminoácidos tales como N-alquil-aminoacetatos y cocoanfodiacetato disódico y óxidos de aminas tales como óxido de estearamina, betaínas, N-alquilamidobetaínas y sus derivados, sultaínas, alquil poliaminocarboxilatos, alquilanfoacetatos, o también tensioactivos siliconados como dimeticona copolioles fosfatos tales como el vendido con la denominación PECOSIL PS 100® por la empresa PHOENIX CHEMICAL y sus mezclas.
Preferentemente, las composiciones según la invención comprenden igualmente un elastómero de silicona anfífilo que contiene grupos, secuencias o injertos hidrófilos polioxialquilenos, en particular polioxietileno y/o polioxipropilenos, o grupos, secuencias o injertos hidrófilos poligliceroles, y que pueden poseer además grupos alquilos laterales, en particular grupos laurilos laterales, principalmente un elastómero de silicona poliglicerolado. A título de ejemplo, se utiliza un organopolisiloxano reticulado elastómero que puede obtenerse por reacción de adición reticulación de diorganopolisiloxano que contiene al menos un hidrógeno unido al silicio y compuestos poliglicerolados que tienen grupos con insaturación etilénica, principalmente en presencia de catalizador platino.
Como elastómeros de silicona poliglicerolados, se pueden utilizar los vendidos con las denominaciones "KSG-710", "KSG-810", "KSG-820", "KSG-830", "KSG-840" por la empresa Shin Etsu.
Medio fisiológicamente aceptable:
Por "medio fisiológicamente aceptable", se entiende designar un medio que conviene particularmente a la aplicación de una composición de la invención sobre la piel, sus apéndices (como por ejemplo cabello, uñas) o labios.
El medio fisiológicamente aceptable se adapta generalmente a la naturaleza del soporte sobre el que debe aplicarse la composición, así como al aspecto sobre el que debe acondicionarse la composición. Este medio puede comprender al menos un disolvente volátil siliconado u orgánico, siendo este disolvente preferentemente compatible con las resinas a/ y b/ y compatible con una utilización cosmética, como se ha especificado anteriormente.
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La composición según la invención puede presentarse en diversas formas, principalmente en forma de polvos (libres
o compactos), de composición anhidra, de dispersión, emulsión, tal como principalmente agua/aceite o agua/cera, aceite/agua, múltiples o cera/agua, o también en forma de gel.
Una composición de la invención es preferentemente una emulsión, en particular directa o inversa, o una composición anhidra.
Una dispersión puede efectuarse en fase acuosa o en fase aceitosa.
Una emulsión puede poseer una fase continua aceitosa o acuosa. Dicha emulsión puede ser, por ejemplo, una emulsión inversa (E/H) o directa (H/E), o también una emulsión múltiple (E/H/E o H/E/H).
En el caso de las emulsiones, se prefieren las emulsiones inversas (E/H).
Una composición anhidra es una composición que contiene menos de 2% en peso de agua, incluso menos de 0,5% de agua, y principalmente exenta de agua. Llegado el caso, también pueden acarrear cantidades bajas de agua principalmente ingredientes de la composición que pueden contener cantidades residuales.
La composición según la invención puede presentarse en la forma de un fluido, por ejemplo, pastoso o líquido. Puede presentarse igualmente en forma de polvo libre o compacto, de pasta flexible, de una crema. Por ejemplo, puede ser una emulsión aceite en agua, agua en aceite o múltiple, emulsión sólida principalmente de tipo agua en aceite, un gel principalmente anhidro, sólido o flexible, en forma de polvo libre o compactado y asimismo en forma bifásica.
La composición según la invención se presenta igualmente en la forma de una composición de maquillaje y/o de cuidado de materias queratínicas, por ejemplo, de una base de maquillaje principalmente para aplicar sobre el rostro
o el cuello, un producto anti-ojeras, un corrector de color, una crema coloreada, un colorete, una barra de labios, un bálsamo de labios, una composición de maquillaje para el cuerpo.
La composición según la invención puede comprender una fase acuosa.
La fase acuosa comprende agua. Un agua que conviene a la invención puede ser un agua floral tal como agua de aciano y/o un agua mineral tal como agua de VITTEL, agua de LUCAS o agua de LA ROCHE POSAY y/o un agua termal.
La fase acuosa puede comprender igualmente disolventes orgánicos miscibles en agua (a temperatura ambiente 250C) como por ejemplo monoalcoholes que tienen de 2 a 6 átomos de carbono tales como etanol, isopropanol; polioles que tienen principalmente de 2 a 20 átomos de carbono, preferentemente que tienen de 2 a 10 átomos de carbono, y preferentemente que tienen de 2 a 6 átomos de carbono, tales como glicerol, propilen glicol, butilen glicol, pentilen glicol, hexilen glicol, dipropilen glicol, dietilen glicol; éteres de glicol (que tienen principalmente de 3 a 16 átomos de carbono) tales como alquil(C1-C4)éter de mono, di o tripropilen glicol, alquil(C1-C4)éteres de mono, di o trietilen glicol, y sus mezclas.
La fase acuosa puede comprender además agentes de estabilización, por ejemplo cloruro de sodio, dicloruro de magnesio y sulfato de magnesio.
La fase acuosa puede comprender igualmente cualquier compuesto hidrosoluble o hidrodispersable compatible con una fase acuosa tales como gelificantes, polímeros filmógenos, espesantes, tensioactivos y sus mezclas.
En particular, una composición de la invención puede comprender una fase acuosa en un contenido que varía de 1% a 80% en peso, principalmente de 5% a 50%, y más particularmente de 10% a 45% en peso respecto al peso total de la composición.
Según otro modo de realización, una composición de la invención puede ser anhidra.
Una composición anhidra puede comprender menos de 5% en peso de agua, respecto al peso total de la composición, y en particular menos de 3%, principalmente menos de 2%, y más particularmente menos de 1% en peso de agua respecto al peso total de la composición.
Más particularmente, una composición anhidra puede estar desprovista de agua.
Una composición cosmética según la presente invención puede comprender al menos una fase grasa líquida y/o sólida.
En particular, una composición de la invención puede comprender al menos una fase grasa líquida, principalmente al menos un aceite como se ha mencionado anteriormente.
Se entiende por aceite, cualquier cuerpo graso en forma líquida a temperatura ambiente (20-250C) y a presión atmosférica.
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Una composición de la invención puede comprender una fase grasa líquida en un contenido que varía de 1 a 90%, en particular de 5 a 80%, en particular de 10 a 70%, y más particularmente, de 20 a 50% en peso respecto al peso total de la composición.
La fase aceitosa que conviene a la preparación de las composiciones cosméticas según la invención puede comprender aceites hidrocarbonados, siliconados, fluorados o no, o sus mezclas.
Los aceites pueden ser volátiles o no volátiles tales como los definidos anteriormente.
Según un modo de realización particular, la fase grasa de la composición según la invención puede no contener compuestos volátiles.
La composición según la invención puede contener igualmente ingredientes utilizados corrientemente en cosmética, tales como vitaminas, espesantes, oligoelementos, calmantes, secuestrantes, perfumes, agentes alcalinizantes o acidificantes, conservantes, filtros solares, tensioactivos, anti-oxidantes, agentes anti-caída del cabello, agentes anticaspa, agentes propulsores, o sus mezclas.
Una composición según la invención puede presentarse, principalmente, en la forma de una composición de maquillaje y/o de cuidado de la piel o de los labios, en particular una base de maquillaje.
Por supuesto, el experto en la técnica se preocupará de elegir este o estos compuestos eventuales complementarios, y/o su cantidad, de manera tal que las propiedades ventajosas de la composición correspondiente según la invención no se alteren, o sustancialmente no se alteren, por la adición considerada.
Según otro aspecto, la invención se refiere igualmente a un conjunto cosmético que comprende:
i) un recipiente que delimita al menos un compartimento, estando dicho recipiente cerrado por un elemento de cierre; y
ii) una composición dispuesta en el interior de dicho compartimento, siendo la composición según la invención.
El recipiente puede tener cualquier forma adecuada. Puede tener principalmente la forma de un frasco, un tubo, un bote, un estuche, una caja, una bolsita o un maletín.
El elemento de cierre puede tener cualquier forma de un tapón amovible, una tapadera, un opérculo, una banda desprendible, o una cápsula, principalmente del tipo que contiene un cuerpo fijado al recipiente y una parte superior articulada sobre el cuerpo. Puede tener igualmente la forma de un elemento que asegura el cierre selectivo del recipiente, principalmente una bomba, válvula, o una clapeta.
El recipiente puede estar asociado a un aplicador, principalmente en forma de una brocha que contiene una organización de pelos mantenidos por un hilo trenzado. Dicha brocha trenzada se describe principalmente en la patente US 4 887 622. Puede tener igualmente la forma de un peine que contiene una pluralidad de elementos de aplicación, obtenidos principalmente de moldeo. Dichos peines se describen por ejemplo en la patente FR 2 796
529. El aplicador puede tener la forma de un pincel, tal como se describe por ejemplo en la patente FR 2 722 380. El aplicador puede tener la forma de un bloque de espuma o de elastómero, de un rotulador, o de una espátula. El aplicador puede estar libre (pompón o esponja) o unido a una varilla portada por el elemento de cierre, tal como se describe por ejemplo en la patente US 5 492 426. El aplicador puede estar unido al recipiente, tal como se describe por ejemplo en la patente FR 2 761 959.
El producto puede estar contenido directamente en el recipiente, o indirectamente. A título de ejemplo, el producto puede estar dispuesto sobre un soporte impregnado, principalmente en forma de una toallita o de un tampón, y dispuesto (en unidad o varios) en una caja o en una bolsita. Dicho soporte que incorpora el producto se describe por ejemplo en la solicitud WO 01/03538.
El elemento de cierre puede estar acoplado al recipiente por atornillamiento. Alternativamente, el acoplamiento entre el elemento de cierre y el recipiente se hace de otra forma que por atornillamiento, principalmente a través de un mecanismo de bayoneta, por encliquetado, fijación, soldadura, pegado, o por atracción magnética. Por "encliquetado" se entiende en particular cualquier sistema que implica el franqueo de un burlete o de un cordón de material por deformación elástica de una parte, principalmente del elemento de cierre, y por retorno a la posición no tensada elásticamente de dicha parte después del franqueo del burlete o del cordón.
El recipiente puede estar realizado al menos en parte en material termoplástico. A título de ejemplos de materiales termoplásticos, se pueden citar polipropileno o polietileno.
Alternativamente, el recipiente se realiza en material no termoplástico, principalmente en vidrio o en metal (o aleación).
El recipiente puede tener paredes rígidas o paredes deformables, principalmente en forma de un tubo o de un frasco en forma de tubo.
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El recipiente puede comprender medios destinados a provocar o facilitar la distribución de la composición. A título de ejemplo, el recipiente puede tener paredes deformables de manera que se provoca la salida de la composición en respuesta a una sobrepresión en el interior del recipiente, sobrepresión que se provoca por aplastamiento elástico (o no elástico) de las paredes del recipiente. Alternativamente, principalmente cuando el producto está en forma de una barra, este última puede ser arrastrada por un mecanismo de pistón. Siempre en el caso de una barra, principalmente de producto de maquillaje (barra de labios, base de maquillaje, etc.), el recipiente puede contener un mecanismo, principalmente de cremallera, o con una varilla aterrajada, o con una rampa helicoidal, y apto para desplazar una barra en dirección de dicha apertura. Un mecanismo como éste se describe por ejemplo en la patente FR 2 806 273 o en la patente FR 2 775 566. Un mecanismo como éste para un producto líquido se describe en la patente FR 2 727 609.
El recipiente puede estar constituido por un maletín con un fondo que delimita al menos un compartimento que contiene la composición, y una tapadera, principalmente articulada sobre el fondo, y apta para recubrir al menos en parte dicho fondo. Un maletín como éste se describe por ejemplo en la patente WO 03/018423 o en la patente FR 2 791 042.
El recipiente puede estar equipado de un escurridor dispuesto cerca de la apertura del recipiente. Un escurridor como éste permite escurrir el aplicador y eventualmente, la varilla a la puede estar unido. Un escurridor como éste se describe por ejemplo en la patente FR 2 792 618.
La composición puede estar a presión atmosférica en el interior del recipiente (a temperatura ambiente) o presurizada, principalmente mediante un gas propulsor (aerosol). En este último caso, el recipiente está equipado de una válvula (del tipo de las utilizadas para los aerosoles).
La composición de la invención puede presentarse en la forma de un producto de cuidado o preferentemente de maquillaje, en particular coloreado, de la piel, más específicamente del rostro como una base de maquillaje, un colorete para las mejillas o párpados, un colorete para las mejillas o párpados, un producto anti-ojeras, un colorete, un polvo libre o compactado, o también un producto de maquillaje del cuerpo como un producto de tatuaje semipermanente o de maquillaje de los labios como una barra de labios, un lápiz de labios o un brillo de labios, que presenta eventualmente propiedades de cuidado o de tratamiento no terapéutico.
Preferentemente, la composición según la invención se presenta en forma de una base de maquillaje.
La composición según la invención puede fabricarse por los procedimientos conocidos, utilizados generalmente en el campo cosmético.
En la solicitud, los contenidos, salvo mención expresa contraria, se expresan en peso respecto al peso total de la composición.
Los ejemplos siguientes tienen como objetivo ilustrar las composiciones y procedimientos según esta invención, pero no son en ningún caso limitativos del alcance de la invención. Todas las partes y porcentajes en los ejemplos son en peso y todas las medidas se han obtenido a aproximadamente 230C, salvo indicación contraria.
Ejemplo Nº1: Obtención de la mezcla de resinas MQ y T propilo según la invención
Materiales
Resina MQ = una resina MQ de fórmula M0,43Q0,57 y de Mn = 3.230 disuelta en xileno al 70,8% en peso de sólidos. La resina MQ se ha fabricado según las técnicas descritas por Daudt en la patente US 2 676 182.
Resina T propilo = una resina de propilo silsesquioxano al 74.8% en peso en tolueno. La resina de propilo silsesquioxano se ha obtenido por hidrólisis de propilo triclorosilano.
Las diferentes disoluciones de resina MQ y de resina T propilo se mezclan en un matraz de tres bocas provisto de un agitador. Se ponen alicuotas de cada mezcla en una cápsula de evaporación de aluminio de 2 pulgadas de diámetro, y se calientan en vacío a una temperatura de 1100C durante una hora, seguido de 1h25 a 1400C. Se hacen observaciones cualitativas visuales sobre la transparencia y dureza de las mezclas obtenidas (véase la tabla 1 siguiente):
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Tabla 1

Ejemplo #

MQ (g) T propilo (g) Alicuota (g) Alicuota seca (g) % en peso de resina MQ Transparencia Dureza

1-a

0,00 13,46 2,0475 1,5361 0,0 Transparente Aspecto goma; sólido blando

1-b

1,40 12,03 2,0643 1,5415 9,9 Transparente Sólido blando

1-c

2,88 16,74 2,0840 1,5517 14,0 Transparente Más duro que 1-b

1-d

4,19 9,39 2,0746 1,5414 29,7 Transparente Más duro que 1-c

1-e

5,72 8,14 2,1066 1,5606 39,9 Transparente Más duro que 1-d

1-f

7,11 6,82 2,0257 1,4968 49,6 Transparente Más duro que 1-e

Los resultados obtenidos muestran la miscibilidad inesperada de las resinas MQ y T propilo, tomando como base la transparencia de la mezcla sin disolvente y la dureza creciente a medida que crece la cantidad de resina MQ.
Según una alternativa nombrada 1-g, se utiliza la mezcla descrita en el ejemplo 22 de la solicitud WO2005/075567 en la que la relación ponderal entre la resina MQ y la resina T propilo es de 85/15.
Según una alternativa nombrada 1-h, se utiliza la mezcla de resinas descrita en el ejemplo 13 de la solicitud WO2007/145765 en la que la relación ponderal entre la resina MQ y la resina T propilo es de 60/40.
Ejemplo 2: Barra de labios líquida

Barra de labios líquida

Mezcla de resinas MQ+T propilo tal como la descrita en el ejemplo 1-d anterior

65,1

CI 77491 y Estearoil Glutamato de Disodio e Hidróxido de Aluminio

2,5

Polidimetilsiloxano 5cSt

4,5

Isododecano

27,9

Ejemplo 3: Barra de labios líquida

Barra de labios líquida

Mezcla de resinas MQ+T propilo tal como la descrita en el ejemplo 1-f anterior

44,1

Aceite de Parleam

10,0

Polidimetilsiloxano 5cSt

20,0

Sílice Pirogenada Hidrófila

1,0

Pigmentos recubiertos perfluorados

2,5

Isododecano

22,4

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Modo de operación

1.

Se realiza un triturado pigmentario de los pigmentos en la fase aceitosa efectuando 3 pasos de la mezcla por la trituradora tricilíndrica

2.

Se pesa en un vaso de precipitados el triturado necesario para la composición, las materias primas no volátiles y las materias primas volátiles.

3.

Se pone la mezcla con agitación RAYNERI durante 45 min.

4.

Se vierte la fórmula en hervidores estancos con isododecano.

Ejemplo 4a: Máscara resistente al agua

Máscara resistente al agua

Mezcla de resinas MQ+T propilo tal como la descrita en el ejemplo 1-f anterior

6

Pigmentos recubiertos PF

6

Cera de abejas

20

Bentona organófila

5,32

Carbonato de propileno

1,74

Isododecano

Csp 100

10
La cera y los pigmentos se calientan hasta la fusión de la cera y la mezcla de homogeneiza, se deja enfriar la mezcla a temperatura ambiente (250C) y se añade la mezcla de resinas (fase A). Paralelamente, se prepara un gel mezclando la bentona, el carbonato de propileno y el isododecano (fase B), se
añade esta mezcla a la fase A a temperatura ambiente y el conjunto se pasa por la trituradora tricilíndrica. 15 Ejemplo 4b: Máscara resistente al agua

Máscara resistente al agua

Mezcla de resinas MQ+T propilo tal como la descrita en el ejemplo 1-f anterior

15

Pigmentos recubiertos NAI

6

Cera de candelilla

25

Polidimetilsiloxano 500 000cSt

15

Ciclopentasiloxano

Csp 100

Los pigmentos y la cera se calientan hasta la fusión de la cera y la mezcla se homogeneiza. Paralelamente, se mezcla el aceite siliconado y la mezcla de resinas a temperatura ambiente (250C), se añade esta mezcla a la mezcla cera/pigmentos a temperatura ambiente, y el conjunto se pasa por la trituradora tricilíndrica. 20 Ejemplo 5: Base de maquillaje
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Base de maquillaje

A1

Pigmentos recubiertos PF 10

Ciclopentasiloxano (D5)

5

A2

Mezcla de resinas MQ+T propilo tal como la descrita en el ejemplo 1-f anterior 10

Oxipropileno en disolución en D5

1,8

Isoestearil digliceril succinato

0,6

Isododecano

CSP 100

D5

5

Poli difenil dimetilsiloxano y ciclopenta dimetil siloxano

3

A3

Polvo de nilón 8

B

Agua 41,4

Conservantes

1

Modo de operación
-Se realiza un triturado pigmentario de pigmentos en la fase aceitosa efectuando 3 pasos de la mezcla A1 por la 5 trituradora tricilíndrica
-Se pesa en un vaso de precipitados el triturado A1 necesario para la composición, las materias primas no volátiles y las materias primas volátiles de la mezcla A2 y A3.
-Se pesa la mezcla B. Se calienta B hasta la obtención de una disolución límpida, y se hace volver la mezcla B a temperatura ambiente.
10 -Se realiza la emulsión añadiendo la mezcla B a la mezcla A1+A2+A3, con agitación Moritz, 1.500 giros/minuto, durante 10 minutos.
Ejemplo 6: Polvo de maquillaje

Polvo de maquillaje

A

Pigmentos recubiertos PF 10

Talco

64,7

Polvo de Nilón

10

Conservante

0,3

B

Aceite de Parleam 8

Mezcla de resinas MQ+T propilo tal como la descrita en el ejemplo 1-f anterior

10

Modo de operación
15 -Se pesan las materias primas de la fase A y se homogeneiza con un mezclador durante 10 minutos. -Se pesan las materias primas de la fase B, que se añade a la fase A. -Se homogeneiza la mezcla en el mezclador durante 3 minutos.
59
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-Se pasa la mezcla A+B por la trituradora Alpine.
Ejemplo 7:
Se han realizado las composiciones siguientes (emulsiones E/H).

Composición

A (recubrimiento NAI invención) B (recubrimiento PF invención) C (recubrimiento Si comparativo)

Nombre INCI

Composición (%)

cetyl PEG/PPG-10/1 dimethicone (Abil EM90 de la empresa Goldschmidt)

2,1 2,1 2,1

polyglyceryl-4 isostearate (ISOLAN GI34® por la empresa EVONIK GOLDSCHMIDT)

2,8 2,8 2,8

A1

hexyl laurate (Cetiol A de Cognis) 2,1 2,1 2,1

Tristearin and Acetylated Glycol Stearate (Unitwix de la empresa United Guardian)

1 1 1

Isododecane

8,25 8,5 8,5

Isododecane

3,5 3,5 3,5

A2

resina MQ/TPropyl 60/40 según el ejemplo 1-h descrito anteriormente 8 8 8

Isododecane Disteardimonium Hectorite and Propylene Carbonate and Isododecane (gel bentona ISD V de Elementis)

8,5 5 8,25 5 8,25 5

CI 77492 Iron oxyde and Disodium Stearoyl Glutamate and Aluminium Hydroxyde (1)

3,8

CI 77491 Iron oxyde and Disodium Stearoyl Glutamate and Aluminium Hydroxyde (2)

1,2 imagen56 imagen57

A3

CI 77499 Iron oxyde and Disodium Stearoyl Glutamate and Aluminium Hydroxyde (3) 0,4 imagen58 imagen59

CI 77891 Titanium Dioxide and Disodium Stearoyl Glutamate and Aluminium Hydroxyde (4)

8,6 imagen60 imagen61

CI 77492 Iron oxyde and C9-15

3,8

Fluoroalcohol Phosphate (5)

CI 77491 Iron oxyde and C9-15

1,2

Fluoroalcohol Phosphate (6)

CI 77499 Iron oxyde and C9-15

0,4

Fluoroalcohol Phosphate (7)

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Composición

A (recubrimiento NAI invención) B (recubrimiento PF invención) C (recubrimiento Si comparativo)

Nombre INCI

Composición (%)

CI 77891 Titanium Dioxide and C9-15 Fluoroalcohol Phosphate (8)

8,6

CI 77492 RECUBRIMIENTO DE TRIETHOXYCAPRYLYLSILANE (9) CI 77491 RECUBRIMIENTO DE TRIETHOXYCAPRYLYLSILANE (10) CI 77499 RECUBRIMIENTO DE TRIETHOXYCAPRYLYLSILANE (11) CI 77891 RECUBRIMIENTO DE TRIETHOXYCAPRYLYLSILANE (12)

3,8 1,2 0,4 8,6

A4

Nylon-12 talco 3,75 3,75 3,75 3,75 3,75 3,75

Agua/disolvente

35,15 35,15 35,15

Phenoyiethanol

0,65 0,65 0,65

B

Methylparaben 0,35 0,35 0,35

Magnesium Sulfate

0,65 0,65 0,65

Caprylyl Glycol

0,45 0,45 0,45

100

100

100

(1)

NAI-C33-9001-10 por la empresa MiYOSHI KASEI

(2)

NAI-C33-8001-10 por la empresa MiYOSHI KASEI

(3)

NAI-C33-7001-10 por la empresa MiYOSHI KASEI 5 (4) NAI-TAO-77891 por la empresa MiYOSHI KASEI

(5)

PFX-5-Sunpuro Yellow C33-9001 por la empresa DAITO KASEI KOGYO

(6)

PFX-5-Sunpuro Red C33-8001 por la empresa DAITO KASEI KOGYO

(7)

PFX-5-Sunpuro Black C33-7001 por la empresa DAITO KASEI KOGYO

(8)

PF 5 TiO2 A 100 por la empresa DAITO KASEI KOGYO 10

(9)

UNIPURE YELLOW LC182 AS EM por la empresa LCW

(10)

UNIPURE RED LC381 AS EM por la empresa LCW

(11)

UNIPURE BLACK LC989 AS-EM por la empresa LCW

(12)

UNIPURE WHITE LC 981 AS-EM por la empresa LCW 15  Modo de operación

Se pesan los constituyentes de la fase A3. La mezcla se pasa sobre trituradora tri-cilíndrica.
Se pesan los constituyentes de la fase A1 en el vaso de precipitados principal y se pone en baño maría (75-800C). Cuando la mezcla es homogénea, se añaden los constituyentes de la fase A2. Después de 5 minutos de agitación en Moritz a 1.500 giros/min, se enfría la mezcla hasta la temperatura ambiente. Se incorpora A3 a la fase A1+A2, con agitación en Moritz a 1.500 giros/min.
Se añaden sucesivamente los constituyentes de la fase A4, manteniendo la misma agitación.
Se pesan los constituyentes de la fase B. Se lleva a ebullición la fase B, hasta la disolución completa de los constituyentes. Se enfría la fase B hasta 500C.
La fase B se añade lentamente en la fase A1+A2+A3+A4, con agitación con Moritz a 3.200 giros/min. La agitación se mantiene durante un mínimo de 10 minutos.
 Protocolo de medidas instrumentales del color inmediato y persistencia del color
Se efectúa una medida colorimétrica de la piel antes y después del maquillaje midiendo los índices Rojo, Amarilo y luminancia, respectivamente a*, b*, L*. Para cada mujer se captó una imagen mediante una Chromasphere, con definición 410x410 píxeles.
Los resultados se expresan de la manera siguiente. El color se cuantifica por los índices Rojo, Amarillo y luminancia analizados por la cámara (respectivamente a*, b*, L*). La persistencia del color se calcula por la variación de estas variables después de 3 horas de maquillaje (deltaE94).
Más precisamente, las medidas se efectúan sobre un panel de personas, que se mantienen en sala de espera climatizada (220C +/-20C) 15 mn antes del inicio del ensayo. Se desmaquillan y se adquiere una imagen de una de sus mejillas mediante la chromasphere con definición 410x410 píxeles. Esta imagen permite medir el color a T0 antes del maquillaje. Después, se pesan aproximadamente 100 mg de composición cosmética en un vidrio de reloj, y se aplican con los dedos desnudos sobre la mitad del rostro sobre la que se ha realizado la medida a T0.
Después de un tiempo de secado de 15 mn, se adquiere una imagen de la mejilla maquillada mediante la Chromasphere. Esta imagen permite medir el color justo después del maquillaje (Timm). Las modelos vuelven a la sala climatizada durante 3 h. Finalmente, se adquiere una imagen de la mejilla maquillada después de 3h de espera mediante la Chromasphere. Esta imagen permite medir el color después de 3 h de maquillaje (T3h).
Los resultados se expresan calculando la diferencia (Timm -T0) que mide el efecto del maquillaje. Se calcula la diferencia (T3h -Timm) que mide la persistencia de este efecto. Cada imagen obtenida mediante la cámara se procesa para color. El color se cuantifica por los índices rojo y amarillo, la luminancia, la diferencia de color (respectivamente a*,b*L y deltaE). Delta E, dE o también ∆E, se define como una medida de diferencia entre dos colores. imagen62
donde:
L1,a1,b1 son las coordenadas en el espacio colorimétrico del primer color a comparar y L2,a2,b2 las del segundo.
 Protocolo de medidas instrumentales de la matidez inmediata y persistencia de la matidez
Se evalúa el efecto de la matidez y persistencia de la matidez de la aplicación, sobre la piel de un panel de personas, de la emulsión E/H descrita anteriormente. La matidez y la persistencia de la matidez pueden medirse mediante el protocolo descrito a continuación. La matidez de una región de la piel, por ejemplo, del rostro se mide mediante una cámara polarimétrica, que es un sistema de formación de imágenes polarimétrico en negro y blanco, con la que se adquieren las imágenes en luz polarizada paralela (P) y cruzada (C). Para el análisis de la imagen resultante de la sustracción de las dos imágenes (P-C), se cuantifica la brillantez midiendo el nivel de gris medio del 5% de píxeles más brillantes correspondientes a las zonas de brillantez.
Más precisamente, las medidas se efectúan sobre un panel de personas, que se mantienen en sala de espera climatizada (220C +/-20C) 15 mn antes del inicio del ensayo. Se desmaquillan y se adquiere una imagen de una de sus mejillas con la cámara polarimétrica. Esta imagen permite medir la brillantez a T0 antes del maquillaje. Después, se pesan aproximadamente 100 mg de la composición descrita anteriormente en un vidrio de reloj, y se aplican con los dedos desnudos sobre la mitad del rostro sobre la que se ha realizado la medida a T0.
Después de un tiempo de secado de 15 mn, se adquiere una imagen de la mejilla maquillada con la cámara polarimétrica. Esta imagen permite medir la brillantez justo después del maquillaje (Timm). Las modelos vuelven a la sala climatizada durante 3 h. Finalmente, se adquiere una imagen de la mejilla maquillada después de 3h de espera mediante la cámara polarimétrica. Esta imagen permite medir la brillantez después de 3 h de maquillaje (T3h). Los resultados se expresan calculando la diferencia (Timm -T0) que mide el efecto del maquillaje. Un valor negativo significa que el maquillaje disminuye la brillantez de la piel y que por lo tanto es matificante.
Se calcula la diferencia (T3h -Timm) que mide la persistencia de este efecto. El valor obtenido debe ser lo más bajo 5 posible lo que significa que la matidez del maquillaje no cambia con el curso del tiempo.
 Protocolo de medidas instrumentales de la homogeneidad inmediata y persistencia de la homogeneidad
Se efectúa una medida colorimétrica de la piel antes y después del maquillaje midiendo las medias para los planos a* (verde-rojo), b* (azul-amarillo), L* (luminancia). Para cada mujer se captó una imagen mediante una Chromasphere, con definición 410x410 píxeles. Más precisamente, las medidas se efectúan sobre un panel de
10 personas, que se mantienen en sala de espera climatizada (220C +/-20C) 15 mn antes del inicio del ensayo. Se desmaquillan y se adquiere una imagen de una de sus mejillas mediante la Chromasphere con definición 410x410 píxeles. Esta imagen permite medir el color a T0 antes del maquillaje. Después, se pesan aproximadamente 100 mg de composición cosmética en un vidrio de reloj, y se aplican con los dedos desnudos sobre la mitad del rostro sobre la que se ha realizado la medida a T0.
15 Después de un tiempo de secado de 15 mn, se adquiere una imagen de la mejilla maquillada mediante la Chromasphere. Esta imagen permite medir el color justo después del maquillaje (Timm). Las modelos vuelven a la sala climatizada durante 3 h. Finalmente, se adquiere una imagen de la mejilla maquillada después de 3h de espera mediante la Chromasphere. Esta imagen permite medir el color después de 3 h de maquillaje (T3h).
Cada imagen obtenida mediante la cámara se explota en coxelografía. Se calcula el tipo de diferencia de cada plan
20 monocromo. El producto de los tres tipos de diferencias es igual al índice coxelográfico. Este parámetro se utiliza para los cálculos estadísticos. Cuanto más homogénea es la piel, más bajo es el tipo de diferencia. El índice coxelográfico evoluciona en el mismo sentido ya que es el producto de tipos de diferencias de los tres planos a*, b* y L*.
Para las medidas efectuadas, se considera que:
25 + efecto ligero o persistencia baja
++ efecto medio o persistencia media
+++ efecto importante o persistencia buena
++++ efecto muy importante o persistencia muy buena
Composiciones
Comportamiento persistencia de la matidez
Comportamiento persistencia del color
Comportamiento persistencia de la homogeneidad

A (recubrimiento NAI)

B (recubrimiento PF) C (recubrimiento Si)

++

++

+

++++

++++

++++

++++

+++ +++

30 Las composiciones presentan un efecto matificante y homogeneizante satisfactorio, incluso muy satisfactorio para los pigmentos NAI.
Las medidas realizadas muestran que en términos de propiedades de persistencia global (matidez, color y homogeneidad), los pigmentos recubiertos NAI y recubiertos PF presentan los mejores resultados.
Reproducimos composiciones según este ejemplo, en las que se reemplaza la mezcla de resinas MQ/TPropilo 60/40
35 según el ejemplo 1-h descrito anteriormente por la mezcla de resinas MQ/TPropilo según el ejemplo 1-f descrito anteriormente, que comprende una relación ponderal MQ/TPropilo de aproximadamente 50/50, con la que se obtienen resultados similares. image31
When the compound of formula (I) comprises a radical R which is an alkyl radical, and therefore a radical R 'having the formula (III), the ratio between nR and nR' is preferably between 5/95 and 95/5, for example
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between 10/90 and 90/10, in particular between 40/60 and 85/15, mainly between 50/50 and 80/20, even between 60/40 and 75/25;
with nR being the number of moles of amine NH2-R and where nR 'is the number of moles of NH2-R' used to prepare the compound of formula (I).
The compounds according to the invention can be in the form of salts and / or isomers of compounds of formula (I).
In general, the compounds of general formula (I) according to the invention can be prepared as described in application FR2910809.
The silicone bis-urea type compounds described above may be mixed with other non-silicone bis10 urea compounds. Non-siliconized bis-urea compounds may, according to a first aspect, respond to the following general formula (II): image32
in which: -A is a group of formula: image33
with R 'being a linear or branched C1 to C4 alkyl radical and * symbolizing the points of attachment of group A to each of the two nitrogen atoms of the remainder of the compound of general formula (II), and
-R is a C6 to C15 alkyl radical, mono-branched, non-cyclic, saturated or unsaturated and whose hydrocarbon chain is eventually interrupted by 1 to 3 heteroatoms chosen from O, S and N, or one of its salts or isomers.
According to a preferred embodiment of the invention, the group represented by A is a group of formula: image34
with R 'and * being as defined above. In particular, R 'can be a methyl group, and group A is more particularly a group of formula: image35
25 with the * being as defined above.
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According to a first embodiment of the invention, R can be chosen from the mono-branched radicals of the general formula CnH2n + 1, where n is an integer ranging from 6 to 15, in particular from 7 to 9 even equal to 8.
Thus, the two R groups of the compound of formula (II) can respectively represent a group: image36
5 with * symbolizing the point of attachment of each of the R groups to each of the nitrogen atoms of the rest of the compound of general formula (II).
According to a second embodiment of the invention, R can be chosen from the mono-branched radicals of the general formula Cm-pH2m + 1-2pXp, p being equal to 1, 2 or 3, preferably equal to 1, m being an integer which varies from 6 to 15, preferably from 10 to 14, in particular from 10 to 12, even equal to 11 and representing X atoms
10 of sulfur and / or oxygen, in particular oxygen atoms.
More particularly, R may be a radical of formula Cm'H2m'X- (Cp'H2p'X ') r-CxH2x + 1, in which X and X' are independently of each other an oxygen or sulfur atom , preferably of oxygen, r is worth 0 or 1, m ', p' and x are integers such that their sum varies from 6 to 15, in particular from 10 to 12, even equals 11 and it is understood that at least one of the carbon chains Cm'H2m ', Cp'H2p', or CxH2x + 1 is branched.
Preferably, it is the CxH2x + 1 chain that is branched, preferably r equal to 0, preferably m 'is an integer ranging from 1 to 10, mainly from 2 to 6, in particular equal to 3, and / or preferably x is an integer that varies from 4 to 16, mainly from 6 to 12, in particular equal to 8.
Thus, the two R groups of the compound of formula (I) can respectively represent a group: image37
20 with * symbolizing the point of attachment of each of the R groups to each of the nitrogen atoms of the rest of the compound of general formula (I).
Said compounds may be present in the compositions according to the invention mixed with isomers, mainly the positional isomers on group A, mainly in the proportions 95/5 or 80/20.
As follows from the following examples, the presence of one or the other of its radicals in the molecule of general formula (II) has been shown to be particularly advantageous in conferring a universal character, in the sense of the invention, on the corresponding non-silicon bis-urea derivatives.
By way of representation and not limitation of the compounds that are particularly suitable for the invention, the following compounds, used pure or in admixture, may be mentioned more particularly:
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And its salts. According to another aspect of the invention, the following non-silicon bis-urea derivatives formula (III): image39
in which: A is a group of formula:
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with -R3 being a hydrogen atom or a linear or branched C1 to C4 alkyl radical, -myn being, independently of each other, equal to 0 or 1, and
5 - * symbolizing the point of attachment of group A to the two nitrogen atoms of the rest of the compound of formula
general (III), -R1 is a C3 to C15 carbon radical, branched, non-cyclic, saturated or unsaturated and possibly containing 1 to 3 heteroatoms chosen from O, S, F and N and / or a carbonyl, and combinations thereof ,
-R2 is different from R1 and is chosen from C1-C24 alkyl radicals, saturated or unsaturated, linear, branched or cyclic, which optionally contains 1 to 3 heteroatoms chosen from O, S, F and N, and eventually substituted with :
-1, 2 or 3 hydroxy radicals, -a ester radical (-COOR4), with R4 being an alkyl radical, linear or branched, having 1 to 8, mainly 1 to 6, even 2 to 4 carbon atoms;
15-a saturated, unsaturated or aromatic cyclic radical having 5 to 12 carbon atoms, in particular a phenyl radical optionally substituted with one or several identical or different radicals chosen from among the C1-C4 alkyl, trifluoromethyl radicals, or a morpholine derivative , I
-one or several C1-C4 linear or branched alkyl radicals,
or one of its salts or isomers.
In particular, n and m are equal, and more particularly equal to zero and R3 is a radical R'3, as defined below. Thus, preferably, A represents a group image41
With R'3 being a linear or branched C1 to C4 alkyl radical and * symbolizing the points of attachment of group A to the two nitrogen atoms of the rest of the compound of general formula (III).
According to a variant of the invention, the compound of general formula (III) comprises, by way of A, at least one group selected from: image42
or
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with R3 'and * being as defined above. In particular, R3 'can be a methyl group, and in this case group A represents a group image44
5th image45
being * as defined above.
In particular, the compounds are such that A is a mixture of 2,4-tolylene and 2,6-tolylene mainly in the proportions (2,4 isomer) / (2,6 isomer) ranging from 95/5 to 80 / twenty.
According to an embodiment of the invention, the compound of the general formula (III) comprises, by way of R1, a branched C6-C15 radical.
According to an embodiment of the invention, the compound of the general formula (III) comprises by way of R1, a group selected from:
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with * symbolizing the point of attachment of the R1 group to the nitrogen of the rest of the compound of general formula (III).
As follows from the following examples, the presence of one and / or the other of its two radicals in the molecule of general formula (III) has been shown to be particularly advantageous in conferring a universal character, in the sense of the invention, to the corresponding asymmetric bis-urea derivatives.
As regards R2 which is different from R1, it can be advantageously chosen from the following groups: image47
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with * symbolizing the point of attachment of the R2 group to the nitrogen of the rest of the compound of general formula (III).
In general, the compounds described can be prepared as described in application FR2910809.
Block Polymers:
5 It is also possible to use grafted block or sequence block polymers as a rheological agent.
Mainly, grafted or sequential block copolymers comprising at least one block of polyorganosiloxane type and at least one block of a radical polymer can be used, such as grafted copolymers of acrylic / silicone type that can be used mainly when the non-aqueous medium is siliconated .
Graft or block copolymers can also be used in sequence comprising at least one block
10 of the polyorganosiloxane type and at least one polyether. The polyorganopolysiloxane block can be mainly a polydimethylsiloxane or a poly (C2-C18) methyl siloxane alkyl; The polyether block may be a C2-C18 poly alkylene, in particular polyoxyethylene and / or polyoxypropylene. In particular, copolyol or C2-C18 alkyl dimethicones copolyol dimethicones such as those sold under the name "Dow Corning 3225C" by Dow Corning, lauryl methicones such as those sold under the name "Dow Corning Q2-5200""by the Dow company
15 Corning.
fifteen
25
35
Four. Five
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As grafted or sequential block copolymers, those comprising at least one block resulting from the polymerization of at least one ethylenic monomer, with one or more eventually conjugated ethylenic bonds, such as ethylene or dienes such as butadiene and isoprene , and of at least one block of a vinyl polymer and better styrenic. When the ethylenic monomer contains several possibly conjugated ethylenic bonds, residual ethylenic unsaturations after polymerization are generally hydrogenated. Thus, in a known manner, the polymerization of the isoprene results, after hydrogenation, with the formation of the ethylene-propylene block, and the polymerization of butadiene results, after hydrogenation, with the formation of the ethylene-butylene block. Among these polymers, one can cite the copolymers in sequence, mainly of the "diblock" or "triblock" type of the polystyrene / polyisoprene (SI), polystyrene / polybutadiene (SB) type such as those sold under the name "LUVITOL HSB" by BASF, of the polystyrene / copoly (ethylene-propylene) (SEP) type such as those sold under the name "Kraton" by Shell Chemical Co or also of the polystyrene / copoly (ethylene-butylene) type (SEB). In particular, Kraton G1650 (SEBS), Kraton G1651 (SEBS), Kraton G1652 (SEBS), Kraton G1657X (SEBS), Kraton G1701X (SEP), Kraton G1702X (SEP), Kraton G1726X (SEB), Kraton D can be used -1101 (SBS), Kraton D-1102 (SBS), Kraton D-1107 (SIS). Polymers are generally referred to as hydrogenated or not hydrogenated dienes copolymers.
You can also use the Gelled Permethyl 99A-750, 99A-753-59 and 99A-753-58 (mixture of tribloque and star polymer), Versagel 5960 of Penreco (tribloque + star polymer); OS129880, OS129881 and OS84383 from Lubrizol (styrene / methacrylate copolymer).
As grafted block or sequence copolymers comprising at least one block resulting from the polymerization of at least one ethylenic monomer with one or more ethylenic bonds and at least one block of an acrylic polymer, bi or three-sequence copolymers can be mentioned poly (methyl methacrylate) / polyisobutylene
or copolymers grafted with poly (methyl methacrylate) skeleton and with polyisobutylene grafts.
As grafted or sequential block copolymers comprising at least one block resulting from the polymerization of at least one ethylenic monomer with one or more ethylenic bonds and at least one block of a polyether such as a C2-C18 polyalkylene (polyethylene and / or polyoxypropylene, mainly), the polyoxyethylene / polybutadiene or polyoxyethylene / polyisobutylene bi or tri-sequence copolymers may be mentioned.
Fat-phase gelling silicone elastomers
"Elastomer" is understood as a lightweight, deformable solid material that has viscoelastic properties and mainly the consistency of a sponge. This elastomer is formed by high molecular weight polymer chains whose mobility is limited by a uniform network of cross-linking points.
The elastomeric organopolysiloxanes used in the composition according to the invention are preferably partially or fully crosslinked. They come in the form of particles. In particular, the elastomeric organopolysiloxane particles have a size ranging from 0.1 to 500 µm, preferably from 3 to 200 µm and better from 3 to 50 µm. These particles can have any shape and for example be spherical, flat or amorphous.
When included in an oily phase, these elastomeric organopolysiloxanes are transformed, according to the oil phase rate used, into a spongy-looking product when used in the presence of low contents in the oily phase, or into a homogeneous gel in the presence of amounts of higher oil phase. The gelation of the oily phase by these elastomers can be total or partial.
Thus, the elastomers of the invention can be transported in the form of an anhydrous gel consisting of an elastomeric organopolysiloxane and an oily phase. The oily phase used during the manufacture of the elastomeric organopolysiloxane anhydrous gel contains one or more liquid oils at room temperature (250C) chosen. between hydrocarbon oils and / or silicone oils. Advantageously, the oily phase is a siliconized liquid phase, which contains one or several oils chosen from the linear or cyclic chain polydimethylsiloxanes, liquid at room temperature that eventually contain an alkyl or aryl side chain or at the end of the chain, the chain having alkyl of 1 to 6 carbon atoms.
According to one mode of application, the elastomeric organopolysiloxanes used according to the invention can be obtained by addition and cross-linking reaction, in the presence of a catalyst, preferably a platinum type catalyst, of at least:
- (i) an organopolysiloxane having two vinyl groups in the α-ω position of the siliconized chain per molecule; Y
- (ii) an organopolysiloxane having at least two hydrogen atoms attached to a silicon atom per molecule.
The first organopolysiloxane (i) is chosen from the polydimethylsiloxanes; it is preferably an α-ω-dimethylvinyl polydimethylsiloxane.
The organopolysiloxane is preferably in a gel obtained according to the following steps:
- (a) mixture of the first and second organopolysiloxanes (i) and (ii);
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- (b) adding an oily phase to the mixture of step (a);
- (c) polymerization of the first and second organopolysiloxanes (i) and (ii) in the oily phase in the presence of a catalyst, preferably a platinum catalyst.
According to one mode of application, the cross-linked organopolysiloxane can be obtained by a polymeric reaction of adding an organohydrogen polysiloxane of formula (I) with an organopolysiloxane of formula (II) and / or an unsaturated hydrocarbon chain of formula (III).
According to a variant, the cross-linked organopolysiloxane is obtained by a polymeric reaction of an organohydrogen polysiloxane of formula (I) with an organopolysiloxane of formula (II).
Organohydrogenpolysiloxane of formula (I)
The organohydrogen polysiloxane of formula (I) comprises at least one structural unit chosen in the group consisting of a SiO2 unit, an HSiO1.5 unit, an RSiO1.5 unit, an RHSiO unit, an R2SiO unit, an R3SiO0.5 unit and a R2HSiO0.5 unit, the R group in these units being a monovalent hydrocarbon chain containing from 1 to 16 carbon atoms that may or may not be substituted but which are different from an unsaturated aliphatic group, and which have an average of at least 1, 5 hydrogen atoms attached to a silicon atom.
The group R in the organohydrogenpolysiloxane of formula (I) may be an alkyl group containing from 1 to 16, preferably from 10 to 16 carbon atoms. This R group can be for example a methyl group, an ethyl group, a propyl group, a lauryl group, a myristyl group and a palmityl group.
The group R in the organohydrogenpolysiloxane of formula (I) can also be an aryl group such as a phenyl or tolyl group.
The group R always in the organohydrogenpolysiloxane of formula (I) can also be a monovalent hydrocarbon chain comprising a cycloalkyl group such as cyclohexyl or a hydrocarbon chain substituted with one, two or several groups chosen from a halogen atom such as chlorine, bromine, fluorine and a cyano group, for example an α-trifluoropropyl or chloromethyl group.
In particular, it is preferred that the group R represents at least 30 mol% of methyl group and 5 to 50 mol%, preferably 10 to 40 mol% of hydrocarbon chain containing from 10 to 16 carbon atoms.
The hydrocarbon chain can advantageously contain at least one lauryl group, even most of the R groups can be lauryl groups.
The organohydrogenpolysiloxane of formula (I) can be linear, branched or cyclic.
The organohydrogen polysiloxane of formula (I) preferably contains from 2 to 50 and even more preferably from 2 to 10 hydrogen atoms bonded to a silicon atom (Si-H). The content of hydrogen atom bound to a silicon atom in this compound of formula (I) varies classically from 0.5 to 50 mol%, and even more preferably from 1 to 20 mol% with respect to the total sum of the hydrogen atoms and all organic groups attached to a silicon atom.
Organopolysiloxane of formula (II)
The organopolysiloxane of formula (II) comprises at least one structural unit chosen from the group consisting of a SiO2 unit, a unit (CH2 = CH) SiO1.5, an RSiO1.5 unit, an R unit (CH2 = CH) SiO, a R2SiO unit, an R3SiO0.5 unit and an R2 unit (CH2 = CH) SiO0.5, the group R being as defined in formula (I) and having on average at least 1.5 vinyl groups attached to a silicon atom.
This compound preferably contains from 2 to 50 vinyl groups attached to a silicon atom. The average number of vinyl groups attached to a silicon atom preferably ranges from 2 to 10, and even more preferably from 2 to 5.
Preferably, at least 30 mol% of the R groups are methyl groups and 5 to 50 mol%, preferably 10 to 40 mol% of the R groups are a hydrocarbon chain containing from 10 to 16 carbon atoms.
The organopolysiloxane of formula (II) can be linear, branched or cyclic.
The vinyl group content in the compound of formula (II) preferably ranges between 0.5 and 50 mol%, even more preferably from 1 to 20 mol% with respect to all organic groups bonded to a silicon atom.
Unsaturated hydrocarbon chain of optional formula (III)
The unsaturated hydrocarbon chain of formula (III) responds to the following formula: image49
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where m is an integer that varies from 2 to 6 and x is an integer at least equal to 1.
5 x is preferably an integer that varies from 1 to 20.
By way of example of this compound of formula (III), one can cite pentadiene, hexadiene, heptadiene, octadiene, pentadecadiene, heptadecadiene and pentatriacontadiene. Polymeric addition reactions are described in detail in US 2004/0234477. Among the cross-linked organopolysiloxanes, cross-linked polyalkyl dimethylsiloxanes are preferred. By polialquil
10 dimethylsiloxane, a linear organopolysiloxane of formula (IV) is understood image50
containing monovalent or divalently attached grafts of formula (V) image51
in which:
Ra is an alkyl group containing from 10 to 16 carbon atoms, and may preferably be a lauryl group, it is already an integer from 1 to 100; za is an integer from 1 to 100; and b is an integer from 1 to 100; zb is an integer from 1 to 100.
20 "Divalently bound" is understood to be linked to two different organopolysiloxanes of formula (IV). It is said
otherwise, a bridge between two linear chains such as those defined by formula (IV). As usable non-emulsifying elastomers according to the invention, the dimethicone / vinyl dimethicone copolymers (INCI name: Dimethicone / Vinyldimethicone crosspolymer) and the vinyl dimethicone / alkyl dimethicone copolymers are preferably used, such as vinyl dimethicone / lauryl dimeticone copolymers (INCI name: Vinyl
25 Dimethicone / Lauryl Dimethicone Crosspolymer). As non-emulsifying elastomers usable according to the invention, there may be mentioned:
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-the name INCI Dimethicone / Vinyldimethicone Crosspolymer (and) C12-14 Pareth 12: as sold with the name "DC 9509" by the company Dow Corning,
-the name INCI Dimethicone / Vinyldimethicone Crosspolymer: such as those sold under the name "DC9505" or "DC 9506" by the company Dow Corning, those named INCI Cyclomethicone (and) Dimethicone / Vinyldimethicone Crosspolymer: as those sold under KSG-15 ® by Shin-Etsu, Methyl Trimethicone (and) Dimethicone / Vinyldimethicone Crosspolymer: as sold by Shin-Etsu under KSG-1610®,
-the name INCI Dimethicone (and) Dimethicone / Vinyldimethicone Crosspolymer: as sold under KSG16® by Shin-Etsu, Isododecane (and) Dimethicone / Vinyldimethicone Crosspolymer: as sold under USG106® by Shin-Etsu,
-INCI name: Vinyl Dimethicone / Lauryl Dimethicone Crosspolymer: KSG-41® (in a mineral oil), KSG42® (in isododecane), KSG-43® (in triethylhexanoine) and KSG-44® (in squalane), sold by Shin-Etsu.
As a non-emulsifying elastomer, there may also be mentioned spherical non-emulsifying silicone elastomers in the form of crosslinked organopolysiloxane powder elastomer coated by silicone resin, mainly of silsesquioxane resin, as described for example in US5538793. Such elastomers are sold under the designations "KSP-100", "KSP-101", "KSP-102", "KSP-103", "KSP-104", "KSP-105" by Shin Etsu.
Other elastomeric crosslinked organopolysiloxanes in the form of spherical powders may be hybridized silicone powders functionalized with fluoroalkyl groups, primarily sold under the designation "KSP-200" by Shin Etsu; hybridized silicone powders functionalized with phenyl groups, mainly sold under the name "KSP-300" by Shin Etsu.
The silicone elastomers with MQ group, such as those sold by the Wacker Company under the designations Belsil RG100, Belsil RPG33 and preferably RG80, can also be used in the compositions according to the invention. These particular elastomers, when in association with the resins according to the invention, can improve the non-transfer properties of the compositions comprising them.
Mention may also be made of lipophilic thickening agents, also called gelling agents, usable in a composition of the invention, ethyl cellulose such as that sold under the name Ethocel® by the company DOW CHEMICAL; polyamide polycondensates resulting from the condensation between a dicarboxylic acid comprising at least 32 carbon atoms and an alkylene diamine and in particular ethylene diamine, wherein the polymer comprises at least one esterified or amidified terminal carboxylic acid group with at least a mono alcohol or a mono amine comprising from 12 to 30 linear and saturated carbon atoms, and in particular, ethylene diamine / stearyl dilinoleate copolymers such as that sold under the name Uniclear 100 VG® by the company ARIZONA CHEMICAL; crosslinked acrylamide polymers and copolymers; galactomannans containing one to six, and in particular two to four, hydroxyl groups with bear, substituted with a saturated or non-saturated alkyl chain, such as guar gum alkylated with C1 to C6 alkyl chains, and in particular C1 to C3, and their mixtures.
As lipophilic thickening agents which are suitable for the invention, there may also be mentioned polystyrene / polyalkylene copolymers, and more particularly copolymers of "diblock", "triblock" or "radial" sequences of polystyrene / polyisoprene, polystyrene / polybutadiene type such as marketed under the name Luvitol HSB® by the company BASF, of the polystyrene / copoly (ethylene-propylene) type such as those sold under the name of Kraton® by the company KRATON POLYMERS or also of the polystyrene / copoly (ethylenebutylene) type, mixtures of tribloque and radial (star) copolymers in isododecane such as those marketed by the company PENRECO with the designation Versagel® such as the mixture of butylene / ethylene / styrene triblock copolymer and of ethylene / propylene / styrene star copolymer in isododecane ( Versagel M 5960).
Among the lipophilic thickeners that can be used in a cosmetic composition of the invention, there may also be mentioned dextrin and fatty acid esters, such as dextrin palmitates, mainly those marketed under the names Rheopearl TL® or Rheopearl KL® by the company CHIBA FLOUR, hydrogenated vegetable oils, such as hydrogenated castor oil, fatty alcohols, in particular C8 to C26, and more particularly C12 to C22, such as, for example, myristyl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, or also polyvinyl alcohol.
Mention may also be made of thickeners, poly (meta) polymers of glyceryl; polyvinylpyrrolidone; associative polymers, and mainly associative polyurethanes; polysaccharide alkyl ether (mainly whose alkyl group contains from 1 to 24 carbon atoms, preferably from 1 to 10, better from 1 to 6, and more especially from 1 to 3) such as those described in EP-A-898958.
Waxes
The composition according to the invention may further comprise at least one wax.
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Wax within the meaning of the present invention means a lipophilic compound, solid at room temperature (250C), with reversible solid / liquid state change, which has a melting point greater than or equal to 300C that can go up to 1200C.
The melting point of the wax can be measured by a differential scanning calorimeter (DSC), for example the calorimeter sold under the designation DSC 30 by the METLER company.
The waxes can be hydrocarbon, fluorinated and / or silicone and have a vegetable, mineral, animal and / or synthetic origin. In particular, the waxes have a melting temperature of greater than 250C and better than 450C.
The wax or the mixture of waxes is present in a content at least equal to 7% by weight. Preferably, it is present in a content ranging from 10 to 40% by weight with respect to the total weight of the composition, better from 15 to 35% and even better from 16 to 30% by weight.
Preferably, the waxes are chosen from beeswax, lanolin wax, and insect waxes from China; rice wax, Carnauba wax, Ouricurry wax, Alfa wax, cork fiber wax, sugarcane wax, Japan wax and sumac wax; montan wax, microcrystalline waxes, paraffins; polyethylene waxes, waxes obtained by Fisher-Tropsch synthesis, waxes obtained by catalytic hydrogenation of animal or vegetable oils that have fatty chains, linear or branched, C8-C32, fluorinated waxes, wax obtained by hydrogenation of esterified olive oil with stearyl alcohol, waxes obtained by hydrogenation of castor oil esterified with cetyl alcohol and sticky waxes.
Mainly hydrocarbon waxes such as beeswax, lanolin wax, and insect waxes from China can be used; rice wax, Carnauba wax, Ouricurry wax, Alfa wax, cork fiber wax, sugarcane wax, Japan wax and sumac wax; montan wax, microcrystalline waxes, paraffins; polyethylene waxes, waxes obtained by the synthesis of Fisher-Tropsch and waxy copolymers as well as their esters.
It is also possible to mention the waxes obtained by catalytic hydrogenation of animal or vegetable oils that have fatty, linear or branched chains, C8-C32.
Among these, one can mention mainly hydrogenated jojoba oil, hydrogenated sunflower oil, hydrogenated castor oil, hydrogenated copra oil and hydrogenated lanolin oil, di- (trimethylol 1,1,1 propane) tetraestearate sold under the name "HEST 2T-4S "by the company HETERENE, tetrabehenate di (trimethylol-1,1,1 propane) sold under the name HEST 2T-4B by the company HETERENE.
You can also cite fluorinated waxes.
It is also possible to use the wax obtained by hydrogenation of olive oil esterified with stearyl alcohol sold under the name "PHYTOWAX Olive 18 L 57" or the waxes obtained by hydrogenation of castor oil esterified with cetyl alcohol sold under the name "PHYTOWAX ricin 16L64 and 22L73 ", by the company SOPHIM. Such waxes are described in application FR-A-2792190.
You can also cite:
- silicone waxes, in particular substituted linear polysiloxanes; there may be mentioned, for example, silicone polyether, alkyl or alkoxy dimethicone waxes having from 16 to 45 carbon atoms, alkyl methicones such as C30-C45 alkyl methicone sold under the trade name "AMS C 30" by DOW CORNING,
-hydrogenated oils specified at 250C such as hydrogenated castor oil, hydrogenated jojoba oil, hydrogenated palm oil, hydrogenated tallow, hydrogenated coconut oil and fatty esters specified at 250C such as C20-C40 alkyl stearate sold under the trade name "KESTER WAX K82H" by the KOSTER KEUNEN company,
-and / or their mixtures.
According to one embodiment, the wax present in the composition according to the invention can be totally or partially in powder form, mainly micronized, to facilitate its application in the preparation of the cosmetic composition.
Among usable waxes in powder form, the Carnauba wax microbeads sold under the name Microcare 350® by the Micro Powders company and the paraffin wax microbeads sold under the name Microease 114S® by the company Micro Powders . Said additional micronized waxes allow mainly to improve the properties during application of the composition on the skin.
Hydrophilic gelling agents:
The composition according to the invention may further comprise at least one hydrophilic gelling agent, also referred to as hydrophilic thickener in the following.
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These thickeners can be used alone or in association. These thickeners can be chosen primarily from gums and cellulosic polymers.
By hydrophilic thickener, is meant a water soluble or dispersible thickening agent.
As hydrophilic thickeners, mention may be made in particular of water-soluble or hydrodispersible thickener polymers. These can be chosen mainly from:
-polyvinylpyrrolidone,
-poly alcohol,
-carboxyvinyl polymers modified or not, such as products marketed under the Carbopol names (CTFA name: carbomer) by Goodrich;
-homo or copolymers of acrylic or methacrylic acids or their salts and esters and in particular products sold under the names VERSICOL F® or VERSICOL K® or Salcare SC95 by the company ALLIED COLLOID, UTRAHOLD 8® by the company CIBA-GEIGY, polyacrylates and polymethacrylates such as products sold under the names of Lubrajel and Norgel by the company GUARDIAN or with the name Hispagel by the company HISPANO CHIMICA, polyacrylic acids of type SYNTHALEN K;
-polyacrylamides;
Acrylic acid and acrylamide copolymers sold in the form of their sodium salt under the names RETEN® by the company HERCULES, sodium polymethacrylate sold under the name DARVAN No. 7® by the company VANDERBILT, the sodium salts of polyhydroxycarboxylic acids sold under the name HYDAGEN F® by the company HENKEL;
-polymers and copolymers of 2-acrylamido 2-methylpropane sulfonic acid, optionally crosslinked and / or neutralized, such as poly (2-acrylamido acid 2-methylpropane sulfonic acid) sold by the company CLARIANT under the name "Hostacerin AMPS" (CTFA name: ammonium polyacryldimethyltauramide);
- crosslinked anionic copolymers of acrylamide and AMPS, which are presented in the form of an E / H emulsion. such as those sold under the name SEPIGEL 305 (name CTFA: Poliacrylamide / C13-14 Isoparaffin / Laureth-7) and under the name SIMULGEL 600 (name CTFA: Acrylamide / Sodium acryloyldimethyltaurate copolymer / Isohexadecane / Polysorbate 80) by the company SEPPIC;
polyacrylic acid copolymers / alkyl acrylates of the PEMULEN type;
Polysaccharide biopolymers such as xanthan gum, guar gum, gum arabic, locust bean gum, acacia gum, scleroglucans, chitin and chitosan derivatives, carrageenans, gelanes, alginates, celluloses such as microcrystalline cellulose, carboxymethylcellulose, hydroxymethylcellulose and hydroxypropyl cellulose;
- hydrophilic pyrogenated silicas obtained by high temperature hydrolysis of a volatile silicon compound in an oxyhydric flame, producing a finely divided silica. Hydrophilic silicas have a significant number of silanol groups on their surface. Such hydrophilic silicas are marketed for example under the names "AEROSIL 130®", "AEROSIL 200®", "AEROSIL 255®", "AEROSIL 300®", "AEROSIL 380®" by the company Degussa, "CAB-O-SIL HS-5® "," CAB-O-SIL EH-5® "," CAB-O-SIL LM-130® "," CAB-O-SIL MS-55® "," CAB-O-SIL M5® "by the company Cabot. They preferably have a particle size that can be nanometric to micrometric, for example, ranging from about 5 to 200 nm;
-hydrophilic clays;
- associative polymers such as COPOLIMERO PEG-150 / STERAIL ALCOHOL / SMDI sold under the name Aculyn 46 by Rohm & Haas, or COPOLÍMERO STEARETH-100 / PEG-136 / HDI sold under the name Rheolate FX 1100 by Elementis);
-and their mixtures.
The hydrophilic thickener can be chosen from the associative polymers. By "associative polymer" within the meaning of the present invention, any amphiphilic polymer is understood to contain in its structure at least one fatty chain and at least one hydrophilic part. The associative polymers according to the present invention can be anionic, cationic, nonionic or amphoteric.
Among the associative anionic polymers, mention may be made of those containing at least one hydrophilic moiety, and at least one fatty chain allyl ether moiety, more particularly among those whose hydrophilic moiety is constituted by an ethylenic unsaturated anionic monomer, more particularly by a Vinyl carboxylic acid and very particularly by an acrylic acid, a matacrylic acid or mixtures thereof, and whose fatty chain allyl ether moiety corresponds to the monomer of the following formula (I): image52
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where R 'designates H or CH3, B designates the ethyleneoxy radical, n is null or designates an integer ranging from 1 to 100, R designates a hydrocarbon radical chosen from the alkyl, arylalkyl, aryl, alkylaryl, cycloalkyl radicals, comprising 8 to 30 carbon atoms, preferably 10 to 24, and more particularly still 12 to 18 carbon atoms.
Anionic amphiphilic polymers of this type are described and prepared, according to an emulsion polymerization process, in EP-0 216 479.
As associative anionic polymers, there may also be mentioned anionic polymers containing at least one hydrophilic moiety of the olefinic unsaturated carboxylic acid type, and at least one hydrophobic moiety exclusively of the alkyl ester (C10-C30) type of unsaturated carboxylic acid. The anionic polymers described and prepared according to US-3 915 921 and 4 509 949 can be cited by way of example.
As cationic associative polymers, there may be mentioned quaternized cellulose derivatives and polyacrylates with amino side groups.
Nonionic associative polymers can be chosen from:
- modified celluloses with groups containing at least one fatty chain such as modified hiroxyethyl celluloses with groups containing at least one fatty chain such as alkyl groups, mainly C8-C22, arylalkyl, alkylaryl, such as NATROSOL PLUS GRADE 330 CS (C16 alkyls ) sold by the AQUALON company,
-celluloses modified with alkyl phenol alkyl glycol ether groups,
- guar gums such as guar hydroxypropyl, modified with groups containing at least one fatty chain such as an alkyl chain,
-polymers of vinyl pyrrolidone and hydrophobic fatty chain monomers;
-polymers of methacrylates or acrylates of C1-C6 alkyls and amphiphilic monomers containing at least one fatty chain,
copolymers of methacrylates or hydrophilic acrylates and hydrophobic monomers containing at least one fatty chain such as, for example, polyethylene glycol methacrylate / lauryl methacrylate copolymer,
associative polyurethanes,
-Your mixes.
Preferably, the associative polymer is chosen from associative polyurethanes. Associative polyurethanes are copolymers of non-ionic sequences that contain in the chain, at the same time, hydrophilic sequences of the most frequently polyoxyethylene nature and hydrophobic sequences that can be single aliphatic chains and / or cycloaliphatic and / or aromatic chains.
In particular, these polymers contain at least two hydrocarbon lipophilic chains, having C6 to C30 carbon atoms, separated by a hydrophilic sequence, the hydrocarbon chains may be side chains or hydrophilic end chains. In particular, it is possible that one or more side chains are provided. In addition, the polymer may contain a hydrocarbon chain at one end or both ends of a hydrophilic sequence. Associative polyurethanes can have sequences in the form of triblock or multiblock. The hydrophobic sequences can therefore be at each end of the chain (for example: triblock copolymer with hydrophilic central sequence) or distributed at the same time at the ends and in the chain (multi-sequence copolymer for example). These polymers can also be grafted or star. Preferably, the associative polyurethanes are triblock copolymers whose hydrophilic sequence is a polyoxyethylene chain containing from 50 to 1,000 oxyethylenated groups. In general, associative polyurethanes contain a urethane bond between the hydrophilic sequences, hence the origin of the name.
As an example of the associative polymers usable in the invention, the polymer C16-OE120-C16 of the company SERVO DELDEN can be mentioned (with the name SER AD FX1100, molecule with urethane function and weight average molecular weight of 1,300), OE being an oxyethylene moiety. As an associative polymer, the Rheolate 205 with urea function sold by the company RHEOX or also Rheolate 208 or 204 or also Rheolate FX 1100 by Elementis can also be used. These associative polyurethanes are sold in pure form. The product DW 1206B of RHOM & HAAS with C20 alkyl chain and urethane bond, sold at 20% in dry matter in water, can also be used.
Solutions or dispersions of these polymers can also be used primarily in water or in hydroalcoholic media. As an example of said polymers, SER AD FX1010, SER AD FX1035 and SER can be mentioned
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AD 1070 of the company SERVO DELDEN, Rheolate 255, Rheolate 278 and Rheolate 244 sold by the company RHEOX. You can also use the product Aculyn 46, DW 1206F and DW 1206J, as well as Acrysol RM 184 or Acrysol 44 from ROHM & HAAS, or Borchigel LW 44 from BORCHERS.
Loads:
The composition according to the invention may further comprise at least one charge.
The load (s) may be present in a content ranging from 0.01% to 50% by weight, based on the total weight of the composition, preferably ranging from 0.01% to 30% by weight.
For charges, particles of any form, colorless or white, mineral or synthetic, insoluble in the medium of the composition must be understood regardless of the temperature at which the composition is manufactured. These charges mainly serve to modify the rheology or texture of the composition.
The charges can be mineral or organic in any way, platelet, spherical or oblong. When they are minerals, they can have any crystallographic form (for example, foil, cubic, hexagonal, orthorhombic, etc.). Talc, mica, silica, kaolin, polyamide powders (Nylon®) (Orgasol® from Atochem), polymethyl methacrylate powders, acrylic polymer, poly-β-alanine and polyethylene powders, polymer polymer powders tetrafluoroethylene (Teflon®), lauroyl-lysine powders, starch powders, cellulose powders, boron nitride, hollow microspheres in organic polymers, mainly polymeric hollow polymers of polyvinylidene / acrylonitrile chloride such as Expancel® (Nobel Industrie), copolymers Acrylic acid (Dow Corning Polytrap®) and silicone resin microbeads (Toshiba Tospearls®, for example), elastomeric polyorganosiloxane particles, precipitated calcium carbonate, magnesium hydrocarbonate carbonate, hydroxyapatite, hollow silica microspheres (Silica Beads® from Maprecos), glass or ceramic microcapsules, clay, quartz, natural diamond dust, metallic soaps derived from organic acids The carboxylics having 8 to 22 carbon atoms, preferably 12 to 18 carbon atoms, for example zinc, magnesium or lithium stearate, zinc laurate, magnesium myristate.
According to a particular way, the association of resins according to the invention with at least one load of a mineral nature, possibly in association with at least one organic load, allows to obtain a product whose termination is smooth and whose cosmetic properties are stable over time, in particular throughout the day. The product is equally sliding on the skin, during application, without a feeling of friction, and gives a soft touch on the skin.
For mineral fillers, talc, mica, kaolin, boron nitride, precipitated calcium carbonate, carbonate and magnesium hydrocarbonate, hydroxyapatite, hollow silica microspheres (Silica Beads® by Maprecos), or glass microcapsules can be mentioned or ceramic, clay, quartz, natural diamond powder or its mixture.
As silica dust, one can cite:
-porous silica microspheres sold under the name SILICA BEADS SB-700 by the company MYOSHI; "SUNSPHERE® H51", "SUNSPHERE® H33" by the company ASAHI GLASS;
- Polydimethylsiloxane coated amorphous silica microspheres sold under the name "SA SUNSPHERE® H33", "SA SUNSPHERE® H53" by the company ASAHI GLASS.
Preferably, the mineral filler is silica, talc or its mixture.
Among spherical charges, silicas are preferred, such as hollow silica microspheres, in particular SB700® from Miyoshi Kasei.
According to a preferred mode, the composition according to the invention further comprises at least one other charge. Said at least one other charge may be mineral or organic. It can thus be a mixture of mineral and organic fillers.
According to an alternative, the composition according to the invention may contain a mineral filler and another mineral filler, said mineral fillers being as defined above, and eventually at least one organic filler, as defined below.
According to another alternative, the composition according to the invention may contain a mineral filler and an organic filler.
For organic fillers, polyamide powders (Nylon® or Orgasol® from Arkema), acrylic polymer powders, mainly polymethyl methacrylate powders, polymethyl methacrylate / ethylene glycol dimethacrylate, allyl polymethacrylate / allyl dimethacrylate / ethylene glycol, ethylene glycol / lauryl methacrylate dimethacrylate copolymer, cellulose, poly-β-alanine and polyethylene powders, tetrafluoroethylene (Teflon®) polymer powders, lauroyl-lysine, starch, hollow polymer microspheres such as of polyvinylidene / acrylonitrile chloride such as Expancel® (Nobel Industrie), acrylic acid copolymers (Polytrap® from Dow Corning) and silicone resin microbeads (Toshiba Tospearls®, for example), elastomeric polyorganosiloxane particles, mainly obtained by polymerization of organopolysiloxane having the
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at least two hydrogen atoms each attached to a silicon atom and an organopolysiloxane comprising at least two groups with ethylenic unsaturation (mainly two vinyl groups) in the presence of platinum catalyst,
or also metallic soaps derived from organic carboxylic acids having from 8 to 22 carbon atoms, preferably from 12 to 18 carbon atoms, for example zinc, magnesium or lithium stearate, zinc laurate, magnesium myristate.
As acrylic polymer powder, it can be mentioned:
-methyl polymethacrylate powders sold under the name COVABEAD® LH85 by the company WACKHERR;
-polymethyl methacrylate / ethylene glycol dimethacrylate powders sold under the name DOW CORNING 5640 MICROSPONGE® SKIN OIL ADSORBER by DOW CORNING; GANZPEARL® GMP-0820 by the company GANZ CHEMICAL;
- ethylene glycol dimethyl methacrylate / ethylene glycol powders sold under the name POLY-PORE® L200, POLY-PORE® E200 by AMCOL;
-ethylene glycol / lauryl methacrylate dimethacrylate copolymer powders sold under the name POLYTRAP® 6603 of the company DOW CORNING.
As elastomeric silicone powder, the powders sold under the names "Trefil® Powder E505C", "Trefil® Powder E-506C" by the company DOW CORNING can be mentioned.
Preferably, the organic filler corresponds to polyamide powders.
In the case where the composition according to the invention comprises mineral fillers and other organic fillers, they can be advantageously in said composition in a ratio of mineral fillers / organic fillers greater than or equal to 1.
To further improve the dullness and the persistence in time of dullness obtained with the compositions comprising the association of resins according to the invention with a load, the load can be chosen from the so-called "sebum absorber" loads. The sebum absorbent charge may be a mineral powder or an organic powder; Silica, polyamide powders (nylon®), acrylic polymer powders, mainly of methyl polymethacrylate, of methyl polymethacrylate / ethylene glycol dimethacrylate, allyl polymethacrylate / ethylene glycol dimethacrylate, ethylene methacrylate / ethylene methacrylate copolymer of lauryl; Polymeric hollow microspheres of polyvinylidene / acrylonitrile chloride, elastomeric silicone powders, mainly obtained by polymerization of organopolysiloxane having at least two hydrogen atoms each attached to a silicon atom and an organopolysiloxane comprising at least two groups with ethylenic unsaturation ( mainly two vinyl groups) in the presence of platinum catalyst.
As polymer hollow microspheres of polyvinylidene / acrylonitrile chloride, those sold under the name Expancel® by Nobel Industrie can be cited.
Coloring matter not treated on surface:
The composition according to the invention may further comprise at least one non-surface treated coloring matter.
The coloring matter can be chosen from the powder coloring matters (mainly pigments and mother of pearl) such as those described above, water-soluble or fat-soluble coloring matters.
Pigments and mother of pearl can be defined as above, but here they are not surface treated with a hydrophobic agent.
On the other hand, water-soluble dyes are, for example, beet juice, methylene blue.
Liposoluble dyes, synthetic or natural, are for example DC Red 17, DC Red 21, DC Red 27, DC Green 6, DC Yellow 11, DC Violet 2, DC Orange 5, Soudan Red, carotenes (β-carotene, lycopene ), xanthophylls (capsantin, capsorubin, lutein), palm oil, Sudan brown, quinoline yellow, bija, curcumin.
Coloring materials, in particular pigments, not treated on the surface may be present in the composition in a content ranging from 0.1% to 50% by weight, based on the total weight of the composition, preferably ranging from 0.5 % to 30% by weight, and preferably ranging from 1% to 20% by weight.
Film-forming polymers
The composition according to the invention may further comprise at least one film forming polymer.
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In the present invention, "film-forming polymer" is understood as a polymer capable of forming it alone or in the presence of an auxiliary film-forming agent, a macroscopically continuous and adherent film on keratinous materials, and preferably a cohesive film, and even better a film whose cohesion and mechanical properties are such that said film can be isolated and manipulable in isolation, for example when said film is made by spilling onto a non-stick surface such as a teflon or siliconized surface.
The film-forming polymers or polymers used, in association with the mixtures of MQ and T-propyl resins, can be transported in the oily phase (fat-soluble or lipo-dispersible polymers) or transported in an aqueous phase (water-soluble or latex polymers).
The composition may contain an aqueous phase and the film forming polymer may be present in this aqueous phase. In this case, this will preferably be an aqueous dispersion polymer (latex) or water soluble.
Among the film-forming polymers usable in the composition of the present invention, there may be mentioned synthetic polymers, radical or polycondensate type, naturally occurring polymers, and mixtures thereof.
As examples of water-soluble film-forming polymers, there are:
-proteins such as proteins of plant origin such as wheat, soy proteins; animal proteins such as keratins, for example keratin hydrolysates and sulfonic keratins;
- cellulose polymers such as hydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose, ethylhydroxyethyl cellulose, carboxymethyl cellulose, as well as quaternized cellulose derivatives;
- acrylic polymers or copolymers, such as polyacrylates or polymethacrylates;
vinyl vinyl polymers, such as polyvinylpyrrolidones, methyl vinyl ether and malic anhydride copolymers, vinyl acetate and crotonic acid copolymer, vinyl pyrrolidone and vinyl acetate copolymers; copolymers of vinyl pyrrolidone and caprolactam; polyvinyl alcohol;
-polymers of chitin or chitosan anionic, cationic, amphoteric or non-ionic,
- Arabic gums, guar gum, xanthan derivatives, karaya gum;
- alginates and carrageenans;
-glycoaminoglycans, hyaluronic acid and its derivatives;
-shellac resin, sandáraca gum, damaras, elemis, copales;
-deoxyribonucleic acid;
-mucopolysaccharides such as chondroitin sulfate,
-and their mixtures.
The film forming polymer may also be present in the composition in the form of particles dispersed in an aqueous phase, generally known as latex or pseudolatex. The preparation techniques of these dispersions are well known to those skilled in the art.
As the aqueous dispersion of film-forming polymer, acrylic dispersions sold under the names Neocryl XK-90®, Neocryl A-1070®, Neocryl A-1090®, Neocryl BT-62®, Neocryl A-1079® and Neocryl A- can be used 523® by AVECIA-NEORESINS, Dow Latex 432® by DOW CHEMICAL, Daitosol 5000 AD® or Daitosol 5000 SJ® by DAITO KASEY KOGYO; Syntran 5760® by Interpolymer Allianz Opt® by Rohm and Hass, aqueous dispersions of acrylic or styrene / acrylic polymers sold under the name of JONCRYL® by JOHNSON POLYMER or also aqueous polyurethane dispersions sold under the denominations Neorez R-981® and Neorez R-974® by AVECIA-NEORESINS, Avalure UR-405®, Avalure UR-410®, Avalure UR-425®, Avalure UR-450®, Sancure 875®, Avalure UR-445® and Sancure 2060® by NEOVEON, Impranil 85® by BAYER, Aquamere H-1511® by HYDROMER; sulfopolyesters sold under the brand name Eastman AQ® by EASTMAN CHEMICAL PRODUCTS, vinyl dispersions such as Mexomere PAM® from CHIMEX, aqueous polyvinyl acetate dispersions such as "Vinybran®" from Nisshin Chemical or marketed by UNION CARBIDE, aqueous dispersions of vinyl pyrrolidone terpolymer, dimethylaminopropyl methacrylamide and lauryl dimethylpropyl methacrylamidoammonium chloride such as Styleze W from ISP, aqueous dispersions of polyurethane / polyacrylic hybrid polymers such as those sold under the references "Hybridur®" or by the company AIR PRODUC®® or Dur company AIR® "from NATIONAL STARCH, core / shell type dispersions: for example those marketed by the company ATOFINA with the reference Kynar (core: fluorinated -coated: acrylic) or also those described in US 5 188 899 (core; silica -coated : silicone) and mixtures thereof.
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The composition may contain an oily phase and the film forming polymer may be present in this oily phase. The polymer may be dispersed or dissolved.
As examples of non-aqueous dispersions of lipodispersible film-forming polymer in the form of non-aqueous dispersions of polymer particles in one or more silicone and / or hydrocarbon oils and which can be stabilized on their surface with at least one stabilizing agent, mainly a sequence polymer , grafted or statistically, the acrylic dispersions in isododecane such as Mexomere PAP® of the CHIMEX company, particle dispersions of a grafted ethylenic polymer, preferably acrylic, in a liquid fatty phase, the ethylenic polymer being advantageously dispersed in the absence of stabilizer Additional surface of the particles such as are mainly described in WO 04/055081.
Among the film-forming polymers usable in the composition of the present invention, there may be mentioned synthetic polymers, of the radical type or of the polycondensate type, naturally occurring polymers, and mixtures thereof.
Radical film forming polymer is understood to mean a polymer obtained by polymerization of monomers with mainly ethylenic unsaturation, each monomer being susceptible to homopolymerization (unlike polycondensates).
The film-forming polymers of the radical type can be mainly polymers, or copolymers, vinyl, mainly acrylic polymers.
Vinyl film-forming polymers can result from the polymerization of monomers with ethylenic unsaturation having at least one acidic group and / or esters of these acidic and / or amide monomers of these acidic monomers.
As the acid group carrier monomer, α, β-ethylenic unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid can be used. Preferably, the (meth) acrylic acid and crotonic acid can be used, and more preferably the (meth) acrylic acid.
The esters of acidic monomers are advantageously chosen from the esters of (meth) acrylic acid (also called (meth) acrylates, mainly (meth) alkyl acrylates, in particular C1-C30 alkyl, preferably C1-C20, (meth) acrylates of aryl, in particular of C6-C10 aryl, (meth) hydroxyalkyl acrylates, in particular of C2-C6 hydroxyalkyl.
Among the (meth) alkyl acrylates, there may be mentioned methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, ethyl-2 hexyl methacrylate, lauryl methacrylate, cyclohexyl methacrylate.
Among the (meth) hydroxyalkyl acrylates, there may be mentioned hydroxyethyl acrylate, 2-hydroxypropyl acrylate, hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate.
Among the (meth) aryl acrylates, benzyl acrylate and phenyl acrylate can be mentioned.
Particularly preferred (meth) acrylic acid esters are alkyl (meth) acrylates.
According to the present invention, the alkyl group of the esters can be either fluorinated, or perfluorinated, that is, that part or all of the hydrogen atoms of the alkyl group are substituted with fluorine atoms.
As amides of the acidic monomers, there may be mentioned, for example, (meth) acrylamides, and mainly N-alkyl (meth) acrylamides, in particular C2-C12 alkyl. Among the N-alkyl (meth) acrylamides, there may be mentioned N-ethyl acrylamide, Nt-butyl acrylamide, Nt-octyl acrylamide and N-undecylacrylamide.
Vinyl film-forming polymers can also result from homopolymerization or copolymerization of monomers chosen from vinyl esters and styrenic monomers. In particular, these monomers may be polymerized with acidic monomers and / or their esters and / or their amides, such as those mentioned above.
As an example of vinyl esters, there may be mentioned vinyl acetate, vinyl neodecanoate, vinyl pivalate, vinyl benzoate and vinyl t-butyl benzoate.
As styrenic monomers, there can be mentioned styrene and alpha-methyl styrene.
Among the film-forming polycondensates, there may be mentioned polyurethanes, polyesters, amide polyesters, polyamides, and epoxy esters, polyureas.
The polyurethanes can be chosen from anionic, cationic, non-ionic or amphoteric polyurethanes, acrylic polyurethanes, polyvinyl pyrrolidones polyurethanes, polyester polyurethanes, polyether polyurethanes, polyureas, polyureapolyurethanes, and mixtures thereof.
Polyesters can be obtained, in a known manner, by polycondensation of dicarboxylic acids with polyols, mainly diols.
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The dicarboxylic acid can be aliphatic, alicyclic or aromatic. Examples of such acids are: oxalic acid, malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, 2,2-dimethylglutaric acid, azelaic acid, subic acid, sebacic acid, fumaric acid, acid maleic acid, itaconic acid, phthalic acid, dodecanedioic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, isophthalic acid, terephthalic acid, 2,5-norbonane dicarboxylic acid, diglycolic acid, thiodipropionic acid, 2,5- naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid. These dicarboxylic acid monomers can be used alone or in combination with at least two dicarboxylic acid monomers. Among these monomers, phthalic acid, isophthalic acid, terephthalic acid can preferably be chosen.
Diol can be chosen from aliphatic, alicyclic, aromatic diols. A diol chosen from: ethylene glycol, diethylene glycol, triethylene glycol, 1,3-propanediol, cyclohexane dimethanol, 4-butanediol is preferably used. Like other polyols, glycerol, pentaerythritol, sorbitol, trimethylol propane can be used.
The amide polyesters can be obtained analogously to the polyesters, by polycondensation of diacids with diamines or amino alcohols. As diamine, ethylenediamine, hexamethylenediamine, meta or paraphenylenediamine can be used. As the amino alcohol, monoethanolamine can be used.
According to an example of a composition according to the invention, the film-forming polymer can be a polymer solubilized in a liquid fatty phase comprising organic oils or solvents (it is said that the film-forming polymer is a fat-soluble polymer). Preferably, the liquid fatty phase comprises a volatile oil, optionally mixed with a non-volatile oil.
As an example of a liposoluble polymer, vinyl ether copolymers can be mentioned (the vinyl group being directly attached to the oxygen atom of the ester group and the vinyl ester having a saturated, linear or branched hydrocarbon radical of 1 to 19 atoms of carbon, attached to the carbonyl of the ester group) and at least one other monomer which can be a vinyl ester (different from the vinyl ester already present), an α-olefin (having 8 to 28 carbon atoms), an alkyl vinyl ether (whose group alkyl contains from 2 to 18 carbon atoms), or an allylic or metalyl ester (having a saturated, linear or branched hydrocarbon radical of 1 to 19 carbon atoms, bonded to the carbonyl of the ester group).
These copolymers can be crosslinked by crosslinkers that can be either vinyl type, allylic or metalyl type, such as tetraalyloxyethane, divinylbenzene, divinyl octanedioate, divinyl dodecanedioate, and divinyl octadecanedioate.
As examples of these copolymers, the copolymers may be mentioned: vinyl acetate / allyl stearate, vinyl acetate / vinyl laurate, vinyl acetate / vinyl stearate, vinyl acetate / octadecene, vinyl acetate / octadecyl vinyl ether, propionate vinyl / allyl laurate, vinyl propionate / vinyl laurate, vinyl stearate / octadecene-1, vinyl acetate / dodecene-1, vinyl stearate / ethyl vinyl ether, vinyl propionate / cetyl vinyl ether, vinyl stearate / acetate allyl, dimethyl-2,2 vinyl octanoate / vinyl laurate, dimethyl-2,2 allyl pentanoate / vinyl laurate, vinyl dimethyl propionate / vinyl stearate, allyl dimethyl propionate / vinyl stearate, vinyl propionate / vinyl stearate, crosslinked with 0.2% divinyl benzene, dimethyl propionate vinyl / vinyl laurate, crosslinked with 0.2% divinyl benzene, vinyl acetate / octadecyl vinyl ether, crosslinked with 0.2% tetraalyloxyethane, vinyl acetate / alil stearate or, crosslinked with 0.2% divinyl benzene, vinyl acetate / octadecene-1 crosslinked with 0.2% divinyl benzene and allyl propionate / allyl stearate crosslinked with 0.2% divinyl benzene.
As supplementary examples of liposoluble film-forming polymers, there can be cited vinyl ester copolymers and at least one other monomer which can be a vinyl ester, mainly vinyl neodecanoate, vinyl benzoate and vinyl t-butyl benzoate, an α-olefin, a alkyl vinyl ether, or an allyl or metalyl ester.
As fat-soluble film-forming polymers, one can also mention the fat-soluble copolymers, and in particular those resulting from copolymerization of vinyl esters having 9 to 22 carbon atoms or acrylates or alkyl methacrylates, the alkyl radicals having 10 to 20 carbon atoms
Said fat-soluble copolymers can be chosen from copolymers of vinyl polystearate, of vinyl polystearate crosslinked by divinylbenzene, of diallyl ether or of diallyl phthalate, copolymers of poly (meth) acrylate of stearyl, of polyvinyl acrylate, of poly (meth) acrylate lauryl, these poly (meth) acrylates can be crosslinked by ethylene glycol or tetraethylene glycol dimethacrylate.
The fat-soluble copolymers defined above are known and are mainly described in application FR-A-2232303; they can have a weight average molecular weight ranging from 2,000 to 500,000 and preferably from
4,000 to 200,000.
As liposoluble film-forming polymers usable in the invention, there may also be mentioned polyalkylenes and mainly copolymers of C2-C20 alkenes, such as polybutene, alkyl celluloses with a linear or branched alkyl radical, saturated or not C1 to C8 as ethyl cellulose and propyl cellulose, copolymers of vinyl pyrrolidone (VP) and mainly copolymers of vinyl pyrrolidone and alkene C2 to C40 and better C3 to C20. As an example of a VP copolymer usable in the invention, there may be mentioned the VP / vinyl acetate, VP / methacrylate copolymer of
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ethyl, butylated polyvinylpyrrolidone (PVP), VP / ethyl methacrylate / methacrylic acid, VP / eicoseno, VP / hexadecene, VP / triacontene, VP / styrene, VP / acrylic acid / lauryl methacrylate.
Mention may also be made of silicone resins, generally soluble or swellable in silicone oils, which are polymers of cross-linked polyorganosiloxanes.
As examples of commercially available polymethylsilylsquioxane resins, those that are marketed by the company Wacker with the reference MK Resin such as Belsil PMS MK, or by the company SHIN-ETSU with the references KR-220L can be cited.
As examples of commercially available polypropylsylesquioxane resins, those which are marketed under the reference DC670 by the company Dow Corning can be mentioned.
As siloxysilicate resins, there can be mentioned trimethylsiloxysilicate (TMS) resins such as those marketed under the SR1000 reference by the General Electric company or with the TMS 803 reference by the Wacker company. Mention may also be made of trimethylsiloxysilicate resins marketed in a solvent such as cyclomethicone, sold under the designation KF-7312J by Shin-Etsu, "DC 749", "DC 593" by Dow Corning.
Mention may also be made of silicone resin copolymers such as those mentioned above with polydimethylsiloxanes, such as pressure-sensitive adhesive copolymers marketed by the Dow Corning company under the reference BIO-PSA and described in US 5 162 410 or also Silicone copolymers resulting from the reaction of a silicone resin, such as those described above, and of a diorganosiloxane such as those described in WO 2004/073626.
Mention may also be made of acrylic / silicone grafted copolymers having a vinyl, methacrylic or acrylic polymer skeleton, and organosiloxane or polyorganosiloxane side grafts. Such polymers are described mainly in US 4 693 935, US 4 981 903, and US 4 981 902.
Preferably, these polymers comprise monomers A, C and optionally B for which:
-A is at least one vinyl polymerizable monomer, methacrylate or free radical acrylate;
-B, when present, is at least one stiffening monomer copolymerizable with A;
-C is a monomer of the following formula: image53
Where X is a vinyl group copolymerizable with monomers A and B;
And it is a divalent connector;
n is 0 or 1;
m is an integer between 1 and 3;
R is a hydrogen atom, an alkyl radical having 1 to 10 carbon atoms, a phenyl radical substituted or not, an alkoxy radical having 1 to 10 carbon atoms;
Z is a monovalent siloxane polymer group.
Examples of monomers A are lower to intermediate esters of methacrylic acid and C1-C12 straight or branched chain alcohols, styrene, vinyl esters, vinyl chloride, vinylidene chloride, or acryloyl monomers.
Examples of B monomers are polar acrylic or methacrylic monomers having at least one hydroxy, amino, ester or ionic group (such as quaternary ammoniums, carboxylate salt or acids such as carboxylic acids, acrylic acids, sulfonic acid or their salts) .
Monomer C has been defined above.
As examples of grafted acrylic / silicone copolymers, those marketed by 3M with the reference 3M Silicones "Plus" VS70 Dry Polymer®, of INCI name: Polysilicone-6, or also KP-561® marketed by SHIN-ETSU and of INCI name: Acrylates / Stearyl Acrylate / Dimethicone Methacrylate Copolymer, KP-562® marketed by SHIN-ETSU and INCI name: Acrylates / Behenyl Acrylate / Dimethicone Acrylate Copolymer.
According to an example of application of the invention, the film-forming polymer is an ethylene polymer of linear film-forming sequences, preferably comprising at least a first sequence and at least a second sequence.
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which have different glass transition temperatures (Tg), said first and second sequence being joined together by an intermediate sequence comprising at least one constituent monomer of the first sequence and at least one constituent monomer of the second sequence.
Advantageously, the first and second sequences and the polymer sequences are incompatible with each other.
Such polymers are described for example in EP 1411069 or WO04 / 028488.
The film-forming polymer can be chosen from among the polymers and / or block or static copolymers that contain mainly polyurethanes, polyacrylics, silicones, fluorinated polymers, butyl gums, copolymers of ethylenes, natural gums and polyvinyl alcohols and mixtures thereof. The monomers of the block or static copolymers comprising at least one association of monomers from which the polymer results at a glass transition temperature below room temperature (250C) can be chosen from mainly butadiene, ethylene, propylene, acrylic, methacrylic , isoprene, isobutene, a silicone and mixtures thereof.
The composition according to the invention can also comprise at least one film-forming polymer chosen from vinyl polymers comprising at least one residue derived from carbosiloxane dendrimer.
The vinyl polymer can mainly have a skeleton and at least one side chain, which comprises a carbosiloxane dendrimer structure. The term "carbosiloxane dendrimer structure" in the context of the present invention represents a molecular structure that has branched groups having high molecular masses, said structure having a high regularity in the radial direction leaving the joint to the skeleton. Said carbosiloxane dendrimer structures are described in the form of a strongly branched siloxanosyl alkylene copolymer in the Japanese patent application placed under public inspection Kokai 9-171
154
The vinyl polymer can be one of the polymers described in the examples of application EP0963751 or for example the product TIB-4-200 marketed by Dow Corning.
The systems with two components such as compounds X and Y, defined below, capable of polymerizing in situ, at atmospheric pressure and ambient temperature, and of forming advantageously biocompatible, non-sticky, slightly opalescent films even can be cited as film-forming polymers. removable Such systems are mainly described in part in patents WO 01/96 450 and GB 2 407 496 of Dow Corning.
According to a particular embodiment, compounds X and compounds Y are siliconized. Compounds X and Y may be amino or non-amino.
According to another embodiment, at least one of the compounds X and Y is a polymer whose main chain consists mostly of organosiloxane units.
Among the silicon compounds mentioned below, some may have both film-forming and adhesive properties, for example their proportion in silicone or according to their use mixed with a particular additive. Consequently, it is possible to modulate the film-forming properties or the adhesive properties of said compounds according to the use considered, this is in particular the case for reactive elastomeric silicones called "room temperature vulcanization".
Compounds X and Y can react together at a temperature that varies between room temperature and 1800C. Advantageously, compounds X and Y are capable of reacting together at room temperature (20 ± 50C) and atmospheric pressure, or advantageously in the presence of a catalyst, by a hydrosilylation reaction or a condensation reaction, or a cross-linking reaction in the presence of a peroxide.
According to a particular embodiment, compounds X and Y react by hydrosilylation in the presence of a catalyst.
Advantageously, compounds X and Y are chosen from siliconized compounds capable of reacting by hydrosilylation in the presence of a catalyst; in particular compound X is chosen from polyorganosiloxanes comprising units of formula (I) described below and compound Y is chosen from organosiloxanes comprising alkylhydrogeno siloxane units of formula (III) described below.
According to a particular embodiment, compound X is a polydimethylsiloxane with terminal vinyl groups, and compound Y is a polymethylhydrogensiloxane.
Compound X is therefore advantageously chosen from polyorganosiloxanes comprising siloxane units of the formula:
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in which:
R represents a monovalent, linear or cyclic hydrocarbon group, comprising from 1 to 30 carbon atoms, preferably from 1 to 20, and better from 1 to 10 carbon atoms, such as a short chain alkyl radical, which comprises for example from 1 to 10 carbon atoms, in particular a methyl radical or also a phenyl group, preferably a methyl radical,
-m is equal to 1 or 2 and
-R 'represents:

or an unsaturated aliphatic hydrocarbon group comprising from 2 to 10, preferably from 3 to 5 carbon atoms such as a vinyl group or a group -R '' - CH = -CHR '''in which R''is a divalent aliphatic hydrocarbon chain, comprising from 1 to 8 carbon atoms, bonded to the silicon atom and R '''is a hydrogen atom or an alkyl radical comprising from 1 to 4 carbon atoms, preferably a hydrogen atom; may be cited as group R 'vinyl groups, allyl and mixtures thereof; or

or an unsaturated cyclic hydrocarbon group comprising from 5 to 8 carbon atoms such as a cyclohexenyl group.

Preferably R 'is an unsaturated aliphatic hydrocarbon group, preferably a vinyl group.
According to one embodiment, R represents an alkyl radical comprising from 1 to 10 carbon atoms or also a phenyl group, and preferably a methyl radical, and R 'is a vinyl group.
Compound Y can be advantageously chosen from polyorganosiloxanes comprising at least one alkylhydrogeno siloxane unit of the following formula; image55
in which:
R represents a monovalent, linear or cyclic hydrocarbon group, comprising from 1 to 30 carbon atoms, such as an alkyl radical having from 1 to 30 carbon atoms, preferably from 1 to 20 and better from 1 to 10 atoms of carbon, in particular a methyl radical, or also a phenyl group and p is equal to 1 or 2. Preferably, R is a hydrocarbon group, preferably methyl.
According to one embodiment, the compositions comprising compound X and / or Y may further comprise an additional reactive compound such as:
-the organic or mineral particles that comprise at least 2 unsaturated aliphatic groups on their surface, for example, surface-treated silica can be mentioned, for example, by siliconized compounds with vinyl groups such as, for example, the treated silica, cytotetramethyltetravinylsiloxane,
-silazan compounds such as hexamethyldisilazane.
The hydrosilylation reaction is carried out in the presence of a catalyst that may be present with one or the other of the compounds X or Y or be present in isolation. For example, this catalyst may be present in the composition in an encapsulated form if the two compounds X and Y, when it should cause interaction, are present in this same composition in a non-encapsulated form or conversely may be present in a non-encapsulated form. encapsulated if at least one of the compounds X and Y is present in the composition in an encapsulated form. The catalyst is preferably based on platinum or tin.
The catalyst may be present in a content ranging from 0.0001% to 20% by weight with respect to the total weight of the composition comprising it.
Compounds X and / or Y may be associated with inhibitors or retarders of polymerization, and more particularly catalyst inhibitors. Non-limitingly, there may be mentioned cyclic polymethyl vinyl siloxanes, and in particular tetravinyl tetramethyl cyclotetrasiloxane, acetylenic alcohols, preferably volatile, such as methyl isobutylol.
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The presence of ionic salts, such as sodium acetate, can have an influence on the polymerization rate of the compounds.
As an example of a combination of compounds X and Y that react by hydrosilylation in the presence of a catalyst, the following references proposed by the Dow Corning company can be cited: DC 7-9800 Soft Skin Adhesive Parts A and B, as well as the combination of mixtures A and B prepared by Dow Corning:
MIX A:

Ingredient (INCI Name)

CAS No. Contents (%) Function

Dimethyl Siloxane, Dimethylvinylsiloxyterminales

68083-19-2 55-95 Polymer

Silica Silycate

68909-20-6 10-40 Load

1,3-Diethenyl-1,1,3,3-Tetramethyldisiloxane complexes

68478-92-2 Catalyst Trace

Tetramethyldivinyldisiloxane

2627-95-4 0.1-1 Polymer

MIX B:

Ingredient (INCI Name)

CAS No. Contents (%) Function

Dimethyl Siloxane, Dimethylvinylsiloxyterminales

68083-19-2 55-95 Polymer

Silica Silycate

68909-20-6 10-40 Load

Dimethyl, Methylhydrogen Siloxane, trimethylsiloxyterminales

68037-59-2 1-10 Polymer

The compound X may represent from 0.1% to 95% by weight with respect to the total weight of the composition containing it, preferably from 1% to 90%, and better from 5% to 80%.
Compound Y may represent from 0.1% to 95% by weight with respect to the total weight of the composition containing it, preferably from 1% to 90%, and better from 5% to 80%.
The composition according to the invention may comprise a plasticizing agent that favors the formation of a film with the film-forming polymer. Said plasticizing agent can be chosen from among all the compounds known to those skilled in the art as being capable of fulfilling the function sought.
Ionic surfactants
The compositions according to the invention may further comprise at least one ionic surfactant.
The surfactant can be lipophilic and / or hydrophilic, used alone or in coupling. The surfactant can be chosen from among the anionic, cationic, amphoteric surfactants.
The surfactant may be present in the composition according to the invention in a content ranging from 0.1% to 10% by weight, based on the total weight of the composition, and preferably ranges from 0.5% to 8% by weight, and preferably it ranges from 0.5% to 7% by weight.
Preferably, the ionic surfactants are chosen from the cationic surfactants, amphoteric surfactants,
25 carboxylates, taurates and N-acyl N-methyl-restaurants, alkyl sulfoacetates, polypeptides, anionic derivatives of alkyl polyglycoside, salts of C16-C30 fatty acids derived from amines, salts of polyoxyethylene fatty acids, phosphoric esters and salts thereof, sulphosuccinates, alkyl sulfates , isethionates and N-acylisethionates, acylglutamates, soy derivatives, citrates, proline derivatives, lactylates, sarcosinates, sulphonates and glycinates.
When the ionic surfactant is an anionic surfactant, it is chosen from:
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-carboxylates, such as sodium 2- (2-Hydroxyalkyloxy) acetate; -services and N-acyl N-methyl restaurants; -alkyl sulfoacetates; -polypeptides; anionic alkyl polyglycoside derivatives (acyl-D-galactoside uronate); - C16-C30 fatty acid salts, mainly those derived from amines, such as triethanolamine stearate and / or
amino-2-methyl-2-propane di-ol-1,3 stearate; -stocks of polyoxyethylene fatty acids mainly those derived from amines or alkaline salts, and mixtures thereof; -phosphoric esters and their salts such as "DEA oleth-10 phosphate" (Crodafos N 10N from CRODA) or
monopotassium monocetyl phosphate (Amphisol K from Givaudan);
-sulfosuccinates such as "Disodium PEG-5 citrate lauryl sulfosuccinate" and "Disodium ricinoleamido MEA sulfosuccinate"; -alkyl sulfates; -isethionates and N-acylisethionates; -acrylic glutamates such as "Disodium hydrogenated tallow glutamate" (AMISOFT HS-21 R® marketed by the
AJINOMOTO company) and sodium stearoyl glutamate (AMISOFT HS-11 PF® marketed by AJINOMOTO company) and mixtures thereof; - soy derivatives such as potassium soyate;
-citrates, such as glyceryl stearate citrate (Axol C 62 Degussa Pellets); - proline derivatives, such as Palmitoil proline sodium (Sepicalm VG from Seppic), or the mixture of Palmitoil sarcosinate sodium, Palmitoyl glutamate magnesium, Palmitic acid and Palmitoyl proline (Sepifeel One from Seppic);
lactylates, such as sodium stearoyl lactylate (Akoline SL from Karlshamns AB);
-sarcosinates, such as palmitoyl sarcosinate sodium (Nikkol sarcosinate PN) or the mixture of Stearoyl sarcosine and Miristoyl sarcosine 75/25 (Crodasin SM de Croda); -sulfonates, such as Alkyl C14-17 sec sodium sulphonate (Hostapur SAS 60 from Clariant); -glycinates, such as cocoyl sodium glycinate (Aminite GCS-12 from Ajinomoto). The compositions according to the invention may also contain one or more amphoteric surfactants such as N
acyl-amino acids such as N-alkyl aminoacetates and disodium cocoanphodiacetate and amine oxides such as stearamine oxide, betaines, N-alkylamidobetaines and their derivatives, sultains, alkyl polyaminocarboxylates, alkylofoacetates, or also silicone surfactants such as dimethicone copolyols such as phosphate phosphate such as phosphate sold under the name PECOSIL PS 100® by the company PHOENIX CHEMICAL and its mixtures.
Preferably, the compositions according to the invention also comprise an amphiphilic silicone elastomer containing hydrophilic polyoxyalkylene groups, sequences or grafts, in particular polyoxyethylene and / or polyoxypropylenes, or polyglycerol hydrophilic groups, sequences or grafts, and which may also have side alkyl groups, in particular lateral lauryl groups, mainly a polyglycerized silicone elastomer. By way of example, an elastomer crosslinked organopolysiloxane is used which can be obtained by cross-linking addition reaction of diorganopolysiloxane containing at least one hydrogen bonded to silicon and polyglycerinated compounds having groups with ethylenic unsaturation, mainly in the presence of platinum catalyst.
As polyglycerized silicone elastomers, those sold under the names "KSG-710", "KSG-810", "KSG-820", "KSG-830", "KSG-840" by Shin Etsu can be used.
Physiologically acceptable medium:
By "physiologically acceptable medium" is meant to designate a medium that is particularly suitable for the application of a composition of the invention on the skin, its appendages (such as hair, nails) or lips.
The physiologically acceptable medium is generally adapted to the nature of the support on which the composition should be applied, as well as to the aspect on which the composition should be conditioned. This medium may comprise at least one silicone or organic volatile solvent, this solvent being preferably compatible with the a / and b / resins and compatible with a cosmetic use, as specified above.
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The composition according to the invention can be presented in various forms, mainly in the form of powders (free
or compact), of anhydrous composition, dispersion, emulsion, such as mainly water / oil or water / wax, oil / water, manifolds or wax / water, or also in gel form.
A composition of the invention is preferably an emulsion, in particular direct or inverse, or an anhydrous composition.
A dispersion can be carried out in the aqueous phase or in the oily phase.
An emulsion may possess an oily or aqueous continuous phase. Said emulsion can be, for example, a reverse (E / H) or direct (H / E) emulsion, or also a multiple emulsion (E / H / E or H / E / H).
In the case of emulsions, inverse emulsions (E / H) are preferred.
An anhydrous composition is a composition that contains less than 2% by weight of water, even less than 0.5% of water, and mainly free of water. Where appropriate, they can also carry low amounts of water, mainly ingredients of the composition that may contain residual amounts.
The composition according to the invention may be in the form of a fluid, for example, pasty or liquid. It can also be presented in the form of a free or compact powder, of flexible paste, of a cream. For example, it may be an oil-in-water, water-in-oil or multiple emulsion, a solid emulsion primarily of the water-in-oil type, a primarily anhydrous, solid or flexible gel, in the form of free or compacted powder and also in two-phase form.
The composition according to the invention is also presented in the form of a make-up and / or care composition of keratin materials, for example, a make-up base mainly for application on the face
or the neck, an anti-dark circles product, a color corrector, a colored cream, a blusher, a lipstick, a lip balm, a makeup composition for the body.
The composition according to the invention may comprise an aqueous phase.
The aqueous phase comprises water. A water suitable for the invention can be a floral water such as cornflower water and / or a mineral water such as VITTEL water, LUCAS water or LA ROCHE POSAY water and / or a thermal water.
The aqueous phase may also comprise water-miscible organic solvents (at room temperature 250C) such as monoalcohols having from 2 to 6 carbon atoms such as ethanol, isopropanol; polyols having mainly 2 to 20 carbon atoms, preferably having 2 to 10 carbon atoms, and preferably having 2 to 6 carbon atoms, such as glycerol, propylene glycol, butylene glycol, pentylene glycol, hexylene glycol , dipropylene glycol, diethylene glycol; glycol ethers (having mainly 3 to 16 carbon atoms) such as (C1-C4) alkyl mono, di or tripropylene glycol ether, (C1-C4) alkyl, mono, di or triethylene glycol ethers, and mixtures thereof .
The aqueous phase may further comprise stabilizing agents, for example sodium chloride, magnesium dichloride and magnesium sulfate.
The aqueous phase may also comprise any water-soluble or hydrodispersible compound compatible with an aqueous phase such as gelling agents, film-forming polymers, thickeners, surfactants and mixtures thereof.
In particular, a composition of the invention may comprise an aqueous phase in a content ranging from 1% to 80% by weight, mainly from 5% to 50%, and more particularly from 10% to 45% by weight with respect to the total weight of the composition.
According to another embodiment, a composition of the invention can be anhydrous.
An anhydrous composition may comprise less than 5% by weight of water, with respect to the total weight of the composition, and in particular less than 3%, mainly less than 2%, and more particularly less than 1% by weight of water with respect to weight Total composition.
More particularly, an anhydrous composition may be devoid of water.
A cosmetic composition according to the present invention may comprise at least one liquid and / or solid fatty phase.
In particular, a composition of the invention may comprise at least one liquid fatty phase, mainly at least one oil as mentioned above.
Oil means any fatty body in liquid form at room temperature (20-250C) and at atmospheric pressure.
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A composition of the invention may comprise a liquid fatty phase in a content ranging from 1 to 90%, in particular from 5 to 80%, in particular from 10 to 70%, and more particularly, from 20 to 50% by weight with respect to to the total weight of the composition.
The oily phase that suits the preparation of the cosmetic compositions according to the invention may comprise hydrocarbon, silicone, fluorinated or not oils, or mixtures thereof.
The oils may be volatile or nonvolatile such as those defined above.
According to a particular embodiment, the fatty phase of the composition according to the invention may not contain volatile compounds.
The composition according to the invention may also contain ingredients commonly used in cosmetics, such as vitamins, thickeners, trace elements, soothing agents, sequestrants, perfumes, alkalizing or acidifying agents, preservatives, sunscreens, surfactants, anti-oxidants, hair loss agents , anti-dandruff agents, propellants, or mixtures thereof.
A composition according to the invention can be presented, mainly, in the form of a makeup and / or skin or lip care composition, in particular a makeup base.
Of course, the person skilled in the art will be concerned with choosing this or these complementary complementary compounds, and / or their quantity, so that the advantageous properties of the corresponding composition according to the invention are not altered, or substantially not altered, by The considered addition.
According to another aspect, the invention also relates to a cosmetic assembly comprising:
i) a container that delimits at least one compartment, said container being closed by a closure element; Y
ii) a composition disposed within said compartment, the composition being according to the invention.
The container can have any suitable shape. It can mainly be in the form of a jar, a tube, a canister, a case, a box, a bag or a briefcase.
The closure element may have any form of a removable cap, a cover, an operculum, a removable band, or a capsule, mainly of the type that contains a body fixed to the container and an articulated upper part on the body. It can also have the form of an element that ensures the selective closure of the container, mainly a pump, valve, or a clapper.
The container may be associated with an applicator, mainly in the form of a brush containing an organization of hairs maintained by a braided thread. Said braided brush is mainly described in US Patent 4 887 622. It can also have the shape of a comb containing a plurality of application elements, obtained mainly from molding. Such combs are described for example in patent FR 2 796
529. The applicator may be in the form of a brush, as described for example in FR 2 722 380. The applicator may be in the form of a foam or elastomer block, a marker, or a spatula. The applicator can be free (pompom or sponge) or attached to a rod carried by the closure element, as described for example in US Patent 5 492 426. The applicator can be attached to the container, as described for example in FR 2 761 959.
The product can be contained directly in the container, or indirectly. By way of example, the product can be arranged on an impregnated support, mainly in the form of a wipe or a buffer, and arranged (in unit or several) in a box or in a sachet. Said support incorporating the product is described for example in the application WO 01/03538.
The closure element may be coupled to the container by screwing. Alternatively, the coupling between the closure element and the container is done other than by screwing, mainly through a bayonet mechanism, by encircling, fixing, welding, gluing, or by magnetic attraction. "Encycling" means in particular any system that involves the postage of a weatherstrip or a cord of material by elastic deformation of a part, mainly of the closure element, and by return to the non-elastically tensioned position of said part after Postage of the weatherstrip or cord.
The container may be made at least in part in thermoplastic material. As examples of thermoplastic materials, polypropylene or polyethylene may be mentioned.
Alternatively, the container is made of non-thermoplastic material, mainly glass or metal (or alloy).
The container may have rigid walls or deformable walls, mainly in the form of a tube or a tube-shaped bottle.
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The container may comprise means intended to cause or facilitate the distribution of the composition. By way of example, the container may have deformable walls so that the composition is exited in response to an overpressure inside the container, overpressure that is caused by elastic (or non-elastic) crushing of the walls of the container. Alternatively, mainly when the product is in the form of a bar, the latter can be dragged by a piston mechanism. Always in the case of a bar, mainly of make-up product (lipstick, make-up base, etc.), the container may contain a mechanism, mainly with a zipper, or with a threaded rod, or with a helical ramp, and suitable for moving a bar in the direction of said opening. A mechanism like this is described, for example, in FR 2 806 273 or in FR 2 775 566. A mechanism like this for a liquid product is described in FR 2 727 609.
The container may consist of a briefcase with a bottom that delimits at least one compartment containing the composition, and a lid, mainly articulated on the bottom, and suitable for covering at least part of said bottom. A briefcase like this is described for example in WO 03/018423 or in FR 2 791 042.
The container may be equipped with a drainer arranged near the opening of the container. A drainer like this allows the applicator to drain and, eventually, the rod to which it can be attached. A drainer like this is described, for example, in FR 2 792 618.
The composition may be at atmospheric pressure inside the vessel (at room temperature) or pressurized, mainly by means of a propellant gas (aerosol). In the latter case, the container is equipped with a valve (of the type used for aerosols).
The composition of the invention can be presented in the form of a care product or preferably a makeup product, in particular colored, of the skin, more specifically of the face as a makeup base, a blush for the cheeks or eyelids, a blush for the cheeks or eyelids, an anti-dark circles product, a blusher, a free or compacted powder, or also a body makeup product such as a semi-permanent tattoo or lip makeup product such as a lipstick, a lipstick or a lip gloss, which eventually has properties of care or non-therapeutic treatment.
Preferably, the composition according to the invention is in the form of a makeup base.
The composition according to the invention can be manufactured by known methods, generally used in the cosmetic field.
In the application, the contents, unless expressly stated otherwise, are expressed by weight with respect to the total weight of the composition.
The following examples are intended to illustrate the compositions and methods according to this invention, but are not in any case limiting the scope of the invention. All parts and percentages in the examples are by weight and all measurements have been obtained at approximately 230C, unless otherwise indicated.
Example No. 1: Obtaining the mixture of MQ and T-propyl resins according to the invention
materials
MQ resin = an MQ resin of formula M0.43Q0.57 and Mn = 3,230 dissolved in 70.8% xylene by weight of solids. The MQ resin has been manufactured according to the techniques described by Daudt in US Patent 2 676 182.
Propyl T-resin = a 74.8% by weight propyl silsesquioxane resin in toluene. The propyl silsesquioxane resin has been obtained by hydrolysis of propyl trichlorosilane.
The different solutions of MQ resin and T-propyl resin are mixed in a three-mouth flask equipped with a stirrer. Aliquots of each mixture are placed in a 2-inch diameter aluminum evaporation capsule, and heated under vacuum at a temperature of 1100C for one hour, followed by 1h25 to 1400C. Qualitative visual observations are made on the transparency and hardness of the mixtures obtained (see table 1 below):
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Table 1

Example #

MQ (g) T propyl (g) Aliquot (g) Dry aliquot (g)% by weight of resin MQ Transparency Hardness

1-a

0.00 13.46 2.0475 1.5361 0.0 Transparent Rubber appearance; soft solid

1 B

1.40 12.03 2.0643 1.5415 9.9 Transparent Soft solid

1 C

2.88 16.74 2,0840 1.5517 14.0 Transparent Harder than 1-b

1-d

4.19 9.39 2.0746 1.5414 29.7 Transparent Harder than 1-c

1-e

5.72 8.14 2.1066 1.5606 39.9 Transparent Harder than 1-d

1-f

7.11 6.82 2.0257 1.4968 49.6 Transparent Harder than 1-e

The results obtained show the unexpected miscibility of the MQ and T-propyl resins, based on the transparency of the solvent-free mixture and the increasing hardness as the amount of MQ resin grows.
According to an alternative named 1-g, the mixture described in example 22 of application WO2005 / 075567 is used in which the weight ratio between the MQ resin and the propyl T resin is 85/15.
According to an alternative named 1-h, the resin mixture described in example 13 of application WO2007 / 145765 is used in which the weight ratio between the MQ resin and the propyl T resin is 60/40.
Example 2: Liquid Lipstick

Liquid Lipstick

Mixture of MQ + T propyl resins as described in example 1-d above

65.1

CI 77491 and Stearoyl Glutamate Disodium and Aluminum Hydroxide

2.5

Polydimethylsiloxane 5cSt

4,5

Isododecane

27.9

Example 3: Liquid Lipstick

Liquid Lipstick

Mixture of MQ + T propyl resins as described in Example 1-f above

44.1

Parleam oil

10.0

Polydimethylsiloxane 5cSt

20.0

Hydrophilic Pyrogenated Silica

1.0

Perfluorinated Coated Pigments

2.5

Isododecane

22.4

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Operation mode

one.

A pigmentary crushing of the pigments in the oily phase is carried out by performing 3 steps of the mixture through the tricylindrical crusher

2.

The crushing necessary for the composition, nonvolatile raw materials and volatile raw materials are weighed into a beaker.

3.

The mixture is placed with RAYNERI stirring for 45 min.

Four.

The formula is poured into airtight kettles with isododecane.

Example 4a: Water resistant mask

Water resistant mask

Mixture of MQ + T propyl resins as described in Example 1-f above

6

PF coated pigments

6

Bee wax

twenty

Organophilic Bentone

5.32

Propylene Carbonate

1.74

Isododecane

Csp 100

10
The wax and pigments are heated until the wax melts and the mixture homogenizes, the mixture is allowed to cool to room temperature (250C) and the resin mixture is added (phase A). In parallel, a gel is prepared by mixing the bentone, propylene carbonate and isododecane (phase B).
add this mixture to phase A at room temperature and the assembly is passed through the three-cylinder crusher. 15 Example 4b: Water resistant mask

Water resistant mask

Mixture of MQ + T propyl resins as described in Example 1-f above

fifteen

NAI coated pigments

6

Candelilla Wax

25

500,000cSt polydimethylsiloxane

fifteen

Cyclopentasiloxane

Csp 100

The pigments and wax are heated until the wax melts and the mixture is homogenized. In parallel, the siliconized oil and the resin mixture are mixed at room temperature (250C), this mixture is added to the wax / pigment mixture at room temperature, and the assembly is passed through the three-cylinder crusher. 20 Example 5: Makeup base
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Makeup base

A1

PF 10 coated pigments

Cyclopentasiloxane (D5)

5

A2

Mixture of MQ + T propyl resins as described in example 1-f above 10

Oxypropylene in solution in D5

1.8

Isostearyl diglyceryl succinate

0.6

Isododecane

CSP 100

D5

5

Poly diphenyl dimethylsiloxane and cyclopenta dimethyl siloxane

3

A3

Nylon Powder 8

B

Water 41.4

Preservatives

one

Operation mode
- A pigmentary crushing of pigments in the oily phase is performed by performing 3 steps of the A1 mixture through the 5-cylinder crusher
-The crushed A1 necessary for the composition, non-volatile raw materials and volatile raw materials of the mixture A2 and A3 are weighed in a beaker.
-Mix B is weighed. B is heated until a clear solution is obtained, and mixture B is returned to room temperature.
10 -The emulsion is made by adding mixture B to the mixture A1 + A2 + A3, with Moritz stirring, 1,500 turns / minute, for 10 minutes.
Example 6: Makeup Powder

Makeup powder

TO

PF 10 coated pigments

talcum powder

64.7

Nylon Powder

10

Preservative

0.3

B

Parleam oil 8

Mixture of MQ + T propyl resins as described in Example 1-f above

10

Operation mode
15 -The raw materials of phase A are weighed and homogenized with a mixer for 10 minutes. -The raw materials of phase B are weighed, which is added to phase A. -The mixture is homogenized in the mixer for 3 minutes.
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-The mixture A + B is passed through the Alpine crusher.
Example 7:
The following compositions have been made (E / H emulsions).

Composition

A (NAI invention coating) B (PF invention coating) C (Comparative Si coating)

INCI Name

Composition (%)

cetyl PEG / PPG-10/1 dimethicone (Abil EM90 from Goldschmidt)

2.1 2.1 2.1

polyglyceryl-4 isostearate (ISOLAN GI34® by EVONIK GOLDSCHMIDT)

2.8 2.8 2.8

A1

hexyl laurate (Cognis Cetiol A) 2.1 2.1 2.1

Tristearin and Acetylated Glycol Stearate (Unitwix of United Guardian)

1 1 1

Isododecane

8.25 8.5 8.5

Isododecane

3.5 3.5 3.5

A2

MQ / TPropyl 60/40 resin according to example 1-h described above 8 8 8

Isododecane Disteardimonium Hectorite and Propylene Carbonate and Isododecane (Elementis ISD V bentone gel)

8.5 5 8.25 5 8.25 5

CI 77492 Iron oxyde and Disodium Stearoyl Glutamate and Aluminum Hydroxyde (1)

3.8

CI 77491 Iron oxyde and Disodium Stearoyl Glutamate and Aluminum Hydroxyde (2)

1.2 image56 image57

A3

CI 77499 Iron oxyde and Disodium Stearoyl Glutamate and Aluminum Hydroxyde (3) 0.4 image58 image59

CI 77891 Titanium Dioxide and Disodium Stearoyl Glutamate and Aluminum Hydroxyde (4)

8.6 image60 image61

CI 77492 Iron oxyde and C9-15

3.8

Fluoroalcohol Phosphate (5)

CI 77491 Iron oxyde and C9-15

1.2

Fluoroalcohol Phosphate (6)

CI 77499 Iron oxyde and C9-15

0.4

Fluoroalcohol Phosphate (7)

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Composition

A (NAI invention coating) B (PF invention coating) C (Comparative Si coating)

INCI Name

Composition (%)

CI 77891 Titanium Dioxide and C9-15 Fluoroalcohol Phosphate (8)

8.6

CI 77492 TRIETHOXYCAPRYLYLSILANE COATING (9) CI 77491 TRIETHOXYCAPRYLYLSILANE COATING (10) CI 77499 TRIETHOXYCAPRYLYLSILANE COATING (11) CI 77891 TRIETHOXYCE (12) COUPLING

3.8 1.2 0.4 8.6

A4

Nylon-12 talc 3.75 3.75 3.75 3.75 3.75 3.75

Water / solvent

35.15 35.15 35.15

Phenoyiethanol

0.65 0.65 0.65

B

Methylparaben 0.35 0.35 0.35

Magnesium Sulfate

0.65 0.65 0.65

Caprylyl Glycol

0.45 0.45 0.45

100

100

100

(one)

NAI-C33-9001-10 by MiYOSHI KASEI

(2)

NAI-C33-8001-10 by MiYOSHI KASEI

(3)

NAI-C33-7001-10 by MiYOSHI KASEI 5 (4) NAI-TAO-77891 by MiYOSHI KASEI

(5)

PFX-5-Sunpuro Yellow C33-9001 by DAITO KASEI KOGYO

(6)

PFX-5-Sunpuro Red C33-8001 by DAITO KASEI KOGYO

(7)

PFX-5-Sunpuro Black C33-7001 by DAITO KASEI KOGYO

(8)

PF 5 TiO2 A 100 by DAITO KASEI KOGYO 10

(9)

UNIPURE YELLOW LC182 AS EM by the company LCW

(10)

UNIPURE RED LC381 AS EM by the company LCW

(eleven)

UNIPURE BLACK LC989 AS-EM by the LCW company

(12)

UNIPURE WHITE LC 981 AS-EM by the company LCW 15  Operation mode

The constituents of phase A3 are weighed. The mixture is passed on tri-cylindrical crusher.
The constituents of phase A1 are weighed in the main beaker and placed in a water bath (75-800C). When the mixture is homogeneous, the constituents of phase A2 are added. After 5 minutes of stirring in Moritz at 1,500 turns / min, the mixture is cooled to room temperature. A3 is incorporated to phase A1 + A2, with stirring in Moritz at 1,500 turns / min.
The constituents of phase A4 are added successively, maintaining the same agitation.
The constituents of phase B are weighed. Phase B is boiled until complete dissolution of the constituents. Phase B is cooled to 500C.
Phase B is added slowly in phase A1 + A2 + A3 + A4, with stirring with Moritz at 3,200 turns / min. Stirring is maintained for a minimum of 10 minutes.
 Instrumental measures protocol for immediate color and color persistence
A colorimetric measurement of the skin is made before and after makeup by measuring the Red, Yellow and luminance indices, respectively a *, b *, L *. For each woman an image was captured using a Chromasphere, with 410x410 pixels definition.
The results are expressed as follows. The color is quantified by the Red, Yellow and luminance indices analyzed by the camera (respectively a *, b *, L *). Color persistence is calculated by the variation of these variables after 3 hours of makeup (deltaE94).
More precisely, the measurements are carried out on a panel of people, who are kept in a heated waiting room (220C +/- 20C) 15 minutes before the start of the test. They remove their makeup and acquire an image of one of their cheeks using the chromasphere with a 410x410 pixel definition. This image allows you to measure the color at T0 before makeup. Then, approximately 100 mg of cosmetic composition is weighed on a watch glass, and applied with the bare fingers on the half of the face on which the measurement has been made at T0.
After a drying time of 15 mn, an image of the cheek made by the Chromasphere is acquired. This image allows you to measure the color just after makeup (Timm). The models return to the heated room for 3 hours. Finally, an image of the makeup cheek is acquired after 3h of waiting by means of the Chromasphere. This image allows you to measure the color after 3 hours of makeup (T3h).
The results are expressed by calculating the difference (Timm -T0) that measures the effect of makeup. The difference (T3h -Timm) that measures the persistence of this effect is calculated. Each image obtained by the camera is processed for color. The color is quantified by the red and yellow indices, the luminance, the color difference (respectively a *, b * L and deltaE). Delta E, dE or also ∆E, is defined as a measure of difference between two colors. image62
where:
L1, a1, b1 are the coordinates in the colorimetric space of the first color to be compared and L2, a2, b2 are those of the second.
 Protocol of instrumental measures of immediate dullness and persistence of dullness
The effect of the maturity and persistence of the maturity of the application, on the skin of a panel of people, of the E / H emulsion described above is evaluated. Dullness and persistence of dullness can be measured by the protocol described below. The dullness of a region of the skin, for example, of the face is measured by a polarimetric camera, which is a polarimetric imaging system in black and white, with which images are acquired in parallel polarized light (P) and cross (C). For the analysis of the image resulting from the subtraction of the two images (PC), the brightness is quantified by measuring the average gray level of 5% of the brightest pixels corresponding to the areas of brightness.
More precisely, the measurements are carried out on a panel of people, who are kept in a heated waiting room (220C +/- 20C) 15 minutes before the start of the test. They remove their makeup and acquire an image of one of their cheeks with the polarimetric chamber. This image allows you to measure the brightness at T0 before makeup. Then, approximately 100 mg of the composition described above is weighed on a watch glass, and applied with the bare fingers on the half of the face on which the T0 measurement was made.
After a drying time of 15 mn, an image of the cheek made with the polarimetric chamber is acquired. This image allows you to measure the brightness right after makeup (Timm). The models return to the heated room for 3 hours. Finally, an image of the makeup cheek is acquired after 3 hours of waiting by means of the polarimetric chamber. This image allows you to measure the brilliance after 3 h of makeup (T3h). The results are expressed by calculating the difference (Timm -T0) that measures the effect of makeup. A negative value means that the makeup decreases the brilliance of the skin and is therefore mattifying.
The difference (T3h -Timm) that measures the persistence of this effect is calculated. The value obtained should be as low as possible 5 which means that the dullness of the makeup does not change over time.
 Instrumental measures protocol for immediate homogeneity and persistence of homogeneity
A colorimetric measurement of the skin is made before and after makeup by measuring the averages for the planes a * (green-red), b * (blue-yellow), L * (luminance). For each woman an image was captured using a Chromasphere, with 410x410 pixels definition. More precisely, the measurements are made on a panel of
10 people, who are kept in a heated waiting room (220C +/- 20C) 15 minutes before the start of the test. They remove their makeup and acquire an image of one of their cheeks using the Chromasphere with definition 410x410 pixels. This image allows you to measure the color at T0 before makeup. Then, approximately 100 mg of cosmetic composition is weighed on a watch glass, and applied with the bare fingers on the half of the face on which the measurement has been made at T0.
15 After a drying time of 15 mn, an image of the cheek made by the Chromasphere is acquired. This image allows you to measure the color just after makeup (Timm). The models return to the heated room for 3 hours. Finally, an image of the makeup cheek is acquired after 3h of waiting by means of the Chromasphere. This image allows you to measure the color after 3 hours of makeup (T3h).
Each image obtained by the camera is exploited in coxelography. The type of difference of each plan is calculated
20 monochrome. The product of the three types of differences is equal to the coxelgraphic index. This parameter is used for statistical calculations. The more homogeneous the skin, the lower the type of difference. The coxelgraphic index evolves in the same direction since it is the product of types of differences of the three planes a *, b * and L *.
For the measures carried out, it is considered that:
25 + light effect or low persistence
++ medium effect or medium persistence
+++ important effect or good persistence
++++ very important effect or very good persistence
Compositions
Persistence of dullness
Color persistence behavior
Homogeneity persistence behavior

A (NAI coating)

B (PF coating) C (Si coating)

++

++

+

++++

++++

++++

++++

+++ +++

The compositions have a satisfactory mattifying and homogenizing effect, even very satisfactory for NAI pigments.
The measurements made show that in terms of properties of global persistence (dullness, color and homogeneity), the NAI coated and PF coated pigments have the best results.
We reproduce compositions according to this example, in which the MQ / TPropyl 60/40 resin mixture is replaced
According to Example 1-h described above by the MQ / TPpropyl resin mixture according to Example 1-f described above, which comprises a weight ratio MQ / TPpropyl of approximately 50/50, with which similar results are obtained.

Claims (13)

1. Cosmetic procedure of makeup and / or care of keratin materials comprising the application on said keratin materials, mainly of the skin, of a composition comprising, in a physiologically acceptable medium: a) a siloxane resin comprising at least 80 mol% of units:

(i)

 (R'3SiO1 / 2) to (hereinafter "M" units) and

(ii)

 (SiO4 / 2) b (hereafter "Q" units) in which  R 'independently represents an alkyl group having 1 to 8 carbon atoms, an aryl group, a

carbinol group or an amino group, with the proviso that at least 95 mol% of the R 'groups are alkyl groups,  a and b have values strictly greater than 0;  and the ratio a / b is between 0.5 and 1.5, b) a propyl silsesquioxane resin comprising at least 80 mol% of units (R''SiO3 / 2) (hereinafter hereinafter "T" units) in which R '' independently represents an alkyl group having 1 to 8 carbon atoms, an aryl group, a carbinol group or an amino group, with the proviso that at least 80 mol% of the R groups '' are propyl groups, the weight ratio between resins a) and b) between 1/99 and 99/1 being comprised, in particular between 85/15 and 15/85, resins a) and b) not being linked to each other by covalent bonds, and the number of units M of the final mixture being strictly less than the number of units (T + Q), and c) at least one powdery coloring matter treated on the surface by a hydrophobic agent chosen from a compound of fluorinated nature, an amino acid, N-acylated amino acids or their salts, and one of their mixtures. 2. Cosmetic procedure of makeup and / or care of keratin materials comprising the application on said keratin materials, mainly of the skin, of a composition comprising, in a physiologically acceptable medium: a) a siloxane resin comprising at least 80 mol% of units:

(i)

 (R'3SiO1 / 2) to (hereinafter "M" units) and

(ii)

 (SiO4 / 2) b (hereafter "Q" units) in which  R 'independently represents an alkyl group having 1 to 8 carbon atoms, an aryl group, a

carbinol group or an amino group, with the proviso that at least 95 mol% of the R 'groups are alkyl groups,  a and b have values strictly greater than 0;  and the ratio a / b is between 0.5 and 1.5, b) a film-forming propyl silsesquioxane resin comprising at least 80 mol% of units (R''SiO3 / 2) (of hereinafter "T" units) in which R '' independently represents an alkyl group having 1 to 8 carbon atoms, an aryl group, a carbinol group or an amino group, with the proviso that at least 40% In moles of the R groups '' are propyl groups, the weight ratio between resins a) and b) being comprised between 1/99 and 99/1, in particular between 85/15 and 15/85, resins a) and b) not being linked to each other by covalent bonds, 64 and the number of units M of the final mixture being strictly less than the number of units (T + Q), Y c) at least one powdery coloring matter treated on the surface by a hydrophobic agent chosen from a compound of fluorinated nature, an amino acid, N-acylated amino acids or their salts, and one of their mixtures. 3. Method according to claim 1 or 2, characterized in that the resins a) and b) of siloxane and propyl silsesquioxane are formulated in the composition through a mixture capable of being obtained according to the following procedure:  Mixing a siloxane resin solution with a propyl silsesquioxane resin solution, and  Heating, under the following specific conditions:  heating homogeneously for at least 1 hour, preferably between 1h and 5h, at a single temperature or at temperature ranges between 900C and 2500C;  with the proviso that this heating is done without the presence of a chemical condensation catalyst between the two resins.

Four.

Process according to any one of the preceding claims, characterized in that said composition is an emulsion, in particular direct or inverse, or an anhydrous composition.

5.

Process according to any one of the preceding claims, characterized in that said composition comprises an amount of resins a) and b) of siloxane in active matter (dry matter), ranging from 0.5 to 60% by weight, based on the total weight of the composition, preferably from 3 to 60% by weight, and better from 4 to 60% by weight.

6.

 Process according to any one of the preceding claims, characterized in that the powdery coloring matter treated on the surface by a hydrophobic agent can be chosen among the pigments, mother-of-pearls and their mixtures.

7.

Process according to any one of the preceding claims, characterized in that the content of said powdery coloring matter treated on the surface by a hydrophobic agent ranges from 0.1 to 50% by weight, with respect to the total weight of the composition, better than 0.5 at 30% by weight.

8.

 Process according to any one of the preceding claims, characterized in that the powdery coloring matter treated on the surface by a hydrophobic agent is chosen from:

-Yellow iron oxide / perfluoroalkyl phosphate, -Red iron oxide / perfluoroalkyl phosphate, -Black iron oxide / perfluoroalkyl phosphate, -The titanium oxide / perfluoroalkyl phosphate, -Yellow iron oxide / perfluoropolymethylisopropyl ether, -The DC Red 7 / perfluoropolymethylisopropyl ether, -The DC Red 6 / PTFE, and its mixture.

9.

Process according to any one of the preceding claims, characterized in that the composition further comprises at least one compound chosen from oils, non-ionic surfactants, amphiphilic silicone elastomers, pasty compounds of non-animal origin, thickener or gelling agents of fatty phase, waxes, hydrophilic gelling agents, fillers, powdery dyes not treated on the surface by a hydrophobic agent, film-forming polymers, ionic surfactants, fibers, and mixtures thereof.

10.

Composition of make-up and / or care of keratin materials, which can be applied in a process according to any one of the preceding claims, comprising, in a physiologically acceptable medium, siloxane resins a) and b) as defined in one of claims 1 to 3 and at least one pulverulent coloring matter surface treated by a hydrophobic agent chosen from a compound of fluorinated nature, an amino acid, N-acylated amino acids or salts thereof, and one of mixtures thereof.

eleven.

Composition according to claim 10, characterized in that the powdered coloring matter surface treated by a hydrophobic agent is as defined in one of claims 6, 7, and 8.

12.

 Cosmetic set comprising:

65

to.

a container that delimits at least one compartment, said container being closed by a closure element; Y

b.

a composition disposed within said compartment, the composition according to claim 10 or 11 being defined.

13. Cosmetic assembly as defined in claim 12 further comprising an applicator in the form of a foam or elastomer block, a marker, or a spatula. 66